JPH11227114A - Laminated molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To heighten the rigidity and transparency of a molding, make its broken pieces developing at its destruction smaller and, at the same time, prevent the broken pieces from being flown apart by a method wherein one or more layers of a resin film are laminated onto a resin base material, in which colloidal silica, the average particle diameter of which is smaller than a specified value, is dispersed substantially under primary particles state. SOLUTION: As a method for obtaining a resin base material, in the matrix resin of which colloidal silica substantially under its primary particle state is dispersed, a melt-forming method after a polymer and the colloidal silica are compounded together by water base, a polymerizing method of the colloidal silica after being dispersed in a radical polymerizable vinyl compound or the like is exampled. As the kind of the matrix resin, in which the colloidal silica is dispersed, various thermoplastic polymers and blendings of two or more of them are exampled. These resin materials are especially favorable in transparency and preferably used for transparent usage. As the colloidal silica, one having the average particle diameter of 50 nm or less is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a powder having an average particle diameter of 50 n.
The present invention relates to a laminated molded article of a resin substrate and a resin film in which colloidal silica of m or less is substantially dispersed in the state of primary particles.

[0002]

2. Description of the Related Art In general, a sheet glass is used as a window material of a transfer body such as an automobile or a railway vehicle. Above all, tempered glass is characterized by small fragments when broken, and laminated glass with a resin film has the feature that further fragments do not scatter, and it is difficult for the occupant to be seriously injured by the fragments, so in modern society Very usefully used.

However, since these glasses are heavy, they limit the fuel efficiency of the transfer body. In addition, since it is difficult to mold into a free shape, the design of the transfer body is restricted. From such a viewpoint, in recent years, there has been a movement to use a transparent resin represented by polymethyl methacrylate or polycarbonate for a window material of a transfer body. Since these transparent resins are light and can be melt-formed or heated and bent, it is possible to obtain molded articles of any shape.

However, these transparent resins have low rigidity when used as a member of a transfer body. In addition, since the broken pieces are large and the cut surface is sharp when broken, there is a problem that the occupant is liable to be seriously injured in the event of a traffic accident or the like. Lamination with a resin film is also performed so that the fragments do not scatter, but no improvement has been seen in the shape of the fragments when broken.

[0005]

That is, conventionally, there has been no molded product which is easy to process, has excellent rigidity, and has small fragments when broken.

An object of the present invention is to provide excellent rigidity and transparency,
Fragments when destroyed are small, and shards do not scatter,
An object of the present invention is to provide a laminated molded product suitable for a window glass of a house or a vehicle.

[0007]

That is, the present invention provides a method for forming a resin film (b) on a resin substrate (a) in which colloidal silica having an average particle diameter of 50 nm or less is substantially dispersed in primary particles. This is a molded product obtained by laminating the above.

Further, the molded article of the present invention comprises a resin film (b) between two resin substrates (a) or between the resin substrate (a) and another type of resin substrate (c). ) May be provided.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As a method for obtaining a resin base material (a) in which colloidal silica used in the present invention is substantially dispersed in a matrix resin in the state of primary particles, WO
No. 96/34036 and Japanese Patent Application No. 8-292029, a method in which polymer particles and colloidal silica are compounded in an aqueous system, followed by melt molding, and a method disclosed in JP-A-5-209927.
And the like. The method includes dispersing the colloidal silica described in Japanese Patent Application Laid-Open Publication No. H11-15095 in a radically polymerizable vinyl compound, followed by polymerization.

Examples of the type of the matrix resin in which the colloidal silica is dispersed include polyethylene, polypropylene, poly-4-methylpentene-1, polymethyl methacrylate, polymethyl methacrylate copolymer (acrylic resin), and acryl rubber core-shell rubber reinforced. Methyl methacrylate-based copolymer, methyl methacrylate-styrene copolymer, polystyrene, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer,
Styrene-maleimide copolymer, rubber-modified styrene-
Maleimide copolymer, rubber reinforced polystyrene (HIP
S), acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-ethylene propylene-styrene resin (AES resin), methyl methacrylate-butadiene-styrene resin (MBS resin), acrylonitrile-butadiene-methyl methacrylate, styrene resin, acrylonitrile- n-butyl acrylate-styrene resin (AAS resin), polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyamide, epoxy resin, polyvinylidene fluoride, polysulfone, ethylene-vinyl acetate copolymer, P
PS resin, polyetheretherketone, PPO resin,
Rubber-modified PPO resin, polyamide-based elastomer, polyester-based elastomer, polybutadiene, butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, polyisoprene, natural rubber, acrylic rubber, ethylene-propylene copolymer, ethylene-propylene-
Diene copolymer, chlorinated butyl rubber, chlorinated polyethylene, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, various thermoplastic polymers such as hydrides of the block copolymer, and the like. Blends of two or more are included.

Among these, a resin base material in which colloidal silica is dispersed in polymethyl methacrylate, a polymethyl methacrylate-based copolymer (acrylic resin), and an acrylic rubber-based core-shell rubber-reinforced methyl methacrylate-based copolymer has particularly high transparency. Good and preferably used for transparent applications.

As the colloidal silica, those having an average particle diameter of 50 nm or less are used, and various commercial products can be used. Even if the colloidal silica having a particle diameter larger than the particle diameter is used, the desired transparency and high rigidity, which are the objectives of the present invention, cannot be simultaneously achieved.

The amount of the colloidal silica and the resin in which the colloidal silica is dispersed is not particularly limited and is selected according to the required performance. However, 1 to 500 parts by weight of silica solids is used per 100 parts by weight of the resin. Preferably, 1 to 150
It is particularly preferred to use parts by weight. The colloidal silica-dispersed resin substrate (a) is prepared by an injection molding method, an extrusion molding method such as a T-die method or an inflation method, a calendar method, a pressure molding method, or the like.
It can be formed into a desired shape by a casting polymerization method or the like.

The resin film (b) used in the present invention includes an acrylic film composed of a pure acrylic resin such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, and polybutyl methacrylate; A film blended with a copolymer, a film composed of a copolymer of an acrylic resin and another resin (for example, a fluorine resin, a polystyrene resin, a polypropylene resin, a polyvinyl chloride resin, a polyester resin, a silicone resin, etc.), and polyvinyl butyral Film, cellophane film, polyethylene film, polypropylene film, polyethylene terephthalate film, polyethylene naphthalate film, nylon film, polystyrene film, Vinyl alcohol film, ethylene - vinyl alcohol copolymer film, polyvinyl chloride film, polyvinylidene chloride film, polyacrylonitrile copolymer film, a polymethylpentene film, a polyethylene - vinyl acetate copolymer film,
Examples include a polycarbonate film, a polyimide film, a polyurethane film, a fluororesin film, and the like, and a laminated film composed of two or more of these. These films may be printed or decorated by printing or the like. A film whose surface is subjected to a surface hardening treatment, an embossing treatment, a matting treatment, or a deposition treatment with a metal or a metal oxide can also be used.

Among these films, an acrylic film made of a pure acrylic resin such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, and polybutyl methacrylate; and a film obtained by blending an acrylic resin with an acrylic rubber-based core-shell multilayer copolymer , Acrylic resin and other resins (for example, fluorine resin, polystyrene resin, polypropylene resin, polyvinyl chloride resin, polyester resin, silicone resin, etc.)
A film of a component comprising a copolymer of the above, a polyvinyl butyral film, a polycarbonate film, a polyurethane film, and a laminated film containing these as one component are suitably used.

These films preferably have a thickness of 10 to 500 μm. Further, it is preferable to use a laminated molded product having excellent tensile toughness with a tensile elongation at break of 10% or more so as not to lower the strength of the laminated molded product. In particular, when obtaining a transparent molded product, the light transmittance is 80% or more and the haze is 5
% Or less of a transparent film is preferably used.

As a method of laminating the colloidal silica-dispersed resin base material (a) and the resin film (b), the base material (a) is formed into a desired shape in advance, and the resin film (a) is heated by a laminator. b) pressure bonding, lamination using an adhesive such as acrylic, urethane or ethylene-vinyl acetate copolymer, or two or more layers of T
Examples of the method include a die and a method of forming a laminate at the same time as film formation by inflation of two or more layers.

In order to form the resin film (b) on the surface of the molded article simultaneously with the injection molding of the resin base material (a), a mold capable of in-mold molding is attached to an injection molding machine, and a film feeding device, The injection molding may be performed after the film is brought into close contact with the inner surface of the cavity of the injection molding die using an apparatus equipped with a film heating plate and a vacuum pump for film suction. Also, after vacuum molding the decorative film in advance by a vacuum molding machine so as to fit the injection mold,
The injection molding may be performed by closely adhering to the inner surface of the mold cavity.

In this manner, a molded article in which the colloidal silica-dispersed resin base material (a) and the resin film (b) are laminated is obtained. In the present invention, both sides of the colloidal silica-dispersed resin base material (a) are used. It may be a molded product obtained by laminating the resin film (b) on the substrate. In addition, a resin film (b) is sandwiched between two colloidal silica-dispersed resin base materials (a).
, Or a molded article provided with a colloidal silica-dispersed resin base material (a) and another type of resin base material (c)
It can also be obtained as a molded product in which the resin film (b) is interposed therebetween.

As the resin of the other type of resin substrate (c), the same resin as the matrix resin in which colloidal silica is dispersed can be used.

Further, in any of the convenient steps in the present invention, additives such as a coloring agent, an ultraviolet absorber, a heat and / or light stabilizer, and a mold release agent are mixed as long as the effects of the present invention are not impaired. Can be used.

[0022]

The present invention will be described below in detail with reference to examples. In the examples, “parts” means “parts by weight” unless otherwise specified. The evaluation methods for physical properties and the like are as follows. 1) Transparency is measured by a haze meter (manufactured by Suga Test Instruments Co., Ltd.
HGM-2DP), the total light transmittance and the haze value were measured using a sample having a thickness of 3 mm according to ASTM D1003. 2) The linear expansion coefficient is SSC manufactured by Seiko Electronic Industry Co., Ltd.
It measured by the TMA method using -5000. 3) For the strength, a bending test was performed according to ASTM D790, and the bending strength and the bending elastic modulus were measured. 4) The form of destruction of the molded product is a test piece of 100 × 100 × 3 mm and weighs 534.8 according to JIS K7211.
g steel ball was dropped from a height of 1 m and observed when broken. 5) The inorganic content in the composite was calculated from the residue when a predetermined amount of the sample was ignited in a crucible. 6) The average particle diameter and the ζ potential of the polymer particles and the ζ potential of the colloidal silica were determined by a dynamic light scattering / laser Doppler electrophoresis apparatus (ELS-80, manufactured by Otsuka Electronics Co., Ltd.).
0).

(Example 1) [Production of colloidal silica-dispersed resin] A separable flask equipped with a condenser, a nitrogen inlet and a stirrer was charged with 200 parts of deionized water and sodium polyoxyethylene alkylphenyl ether terphosphate as an emulsifier. Salt (manufactured by Toho Chemical Industry Co., Ltd., trade name: GAFAC LO-
529) 1.25 parts, sodium ethylenediaminetetraacetate 0.0003 part, sodium formaldehyde sulfoxylate 0.2 part, and ferrous sulfate 0.0001 part were added, and the temperature was raised to 75 ° C. with stirring. A mixture of 90 parts of methyl methacrylate, 10 parts of methyl acrylate, 0.5 part of γ-mercaptopropyltrimethoxysilane and 0.125 part of tert-butyl hydroperoxide was added dropwise thereto over 3 hours. After completion of the dropwise addition, the mixture was kept at 75 ° C. for 1 hour to obtain an aqueous latex of polymer particles. The average particle size of the polymer particles determined by dynamic light scattering (DLS) is 90.
nm, the ζ potential was -28 mV, and the particles were negatively charged.

Next, when the average particle size is 15 nm,
125 parts of a colloidal silica aqueous dispersion (silica content: 20% by weight, manufactured by Nissan Chemical Industries, Ltd.) having a potential of -17 mV (silica content: 25 parts) were added, and 1.25 parts of dimethyldimethoxysilane was added. C. for 1 hour. According to DLS measurement after this step, the average particle size was 105
nm, and an increase in particle size was observed.

After cooling the reaction system, the content was poured into 500 parts of warm water in which 5 parts of calcium acetate were dissolved, and subjected to salting out and coagulation to separate a powdery composite. Thereafter, the powdery composite was thoroughly washed with water and dried at 90 ° C. for 24 hours.
The recovery of this powdery composite was 97%, the inorganic content in the composite was 21% by weight, and the added colloidal silica was quantitatively introduced into the composite. According to a transmission electron micrograph of this composite, methyl methacrylate-
15n particle size around methyl acrylate copolymer particles
m colloidal silica was observed to be attached in the form of primary particles.

The powdery composite was extruded at a cylinder temperature of 220 ° C. using a twin-screw extruder to obtain pellets. According to a transmission electron micrograph of a sample obtained by press-molding the pellet at a mold temperature of 220 ° C.,
It was observed that colloidal silica particles having a primary particle diameter of 15 nm were uniformly dispersed without agglomeration. [Lamination with Resin Film (b)] A 500 μm-thick single-sided surface-cured polycarbonate film (manufactured by Mitsubishi Engineering-Plastics Corporation, trade name Iupilon MR-
05, elongation at break 120%, light transmittance 90%, haze value 1
%) Is composed of a movable mold and a fixed mold, and the thickness of the molded product is 3%.
The surface hardened surface is placed in the injection molding die having a cavity of 100 × 100 mm set to be mm, facing the movable die surface, and vacuum suction is performed while heating at 80 ° C. Then, the movable mold was brought into close contact with the inner surface of the cavity. After closing the mold, while maintaining the mold temperature at 60 to 80 ° C, the molten resin comprising the composite obtained above heated to 220 to 240 ° C was injected into the mold to solidify the resin. Thereafter, the molding die was opened and the resin molded product was taken out. This molded product had a structure in which a surface-cured polycarbonate film (b) was laminated on one side of a colloidal silica-dispersed resin base material (a) such that the cured surface thereof faced. [Evaluation] Table 1 shows the evaluation results of the obtained molded articles. As is clear from the table, the molded product was excellent in transparency and rigidity. The fracture mode when the steel ball was dropped and fractured was as shown in Fig. 1 and it contained radial cracks and concentric cracks, and the fragments were very fine, but almost scattered I never did.

Example 2 214 parts of a colloidal silica aqueous dispersion having an average particle diameter of 25 nm and a ζ potential of −40 mV (silica content 20% by weight, manufactured by Nissan Chemical Industries, Ltd.) (silica content 43%) Parts) and the amount of dimethyldimethoxysilane was 2.15 parts, and a composite was produced in exactly the same manner as in Example 1. According to DLS measurement, the average particle size of the composite was 120 nm. Also,
The recovery of the powdery composite after separation, washing and drying was 98% and the inorganic content was 30% by weight in the same manner as in Example 1.
Met. Observation of a sample press-molded in the same manner as in Example 1 using this powdery composite showed that colloidal silica particles having a primary particle diameter of 25 nm were uniformly dispersed without agglomeration.

Using a 200 μm-thick polycarbonate film (manufactured by Mitsubishi Engineering-Plastics Co., Ltd., trade name Iupilon FE-2000) and the composite obtained above, it was confirmed that the molded product had a thickness of 1.5 mm. Except for the above, a molded product having a thickness of 1.5 mm in which a polycarbonate film was laminated on one side was obtained in the same manner as in Example 1. This molded product is placed in an injection molding die having a cavity of 100 × 100 mm set to have a thickness of 3 mm so that the polycarbonate film surface faces the fixed die (injection side). Vacuum suction was performed while heating at a temperature of ° C, and the movable mold was brought into close contact with the inner surface of the cavity. After closing the mold, while keeping the mold temperature at 60-80 ° C,
The molten resin composed of the composite obtained above heated to 220 ° C. to 240 ° C. was injected into a mold to solidify the resin. Thereafter, the molding die was opened and the resin molded product was taken out. The laminated molded product is a colloidal silica-dispersed resin base material (a)
Had a structure in which the polycarbonate film (b) was sandwiched between them. Table 1 shows the evaluation results of the obtained molded articles. As is clear from the table, the obtained molded article was excellent in transparency and rigidity. The fracture mode when the steel ball was dropped and fractured was as shown in Fig. 2 and concentric cracks as well as radial cracks were contained. I never did.

Example 3 A molded article having a thickness of 1.5 mm and having a polycarbonate film laminated on one side was obtained in the same manner as in Example 2 except that the colloidal silica dispersion resin produced in Example 1 was used. Was. Thereafter, this was placed in a mold for injection molding, and the same as in Example 2 except that polymethyl methacrylate (trade name: Acrypet VH, manufactured by Mitsubishi Rayon Co., Ltd.) was used instead of the colloidal silica dispersion resin. A laminated molded product was manufactured. This laminated molded product had a structure in which a polycarbonate film (b) was sandwiched between a colloidal silica-dispersed resin substrate (a) and a polymethyl methacrylate substrate (c).

Table 1 shows the evaluation results of the obtained molded articles. As is clear from the table, this molded product was also excellent in transparency and rigidity. The fracture mode when the steel ball was dropped and fractured was as shown in FIG. 3, which contained radial cracks and concentric cracks, and the fragments were very fine, but almost scattered I never did.

Comparative Example 1 A structure in which a polycarbonate film was laminated on polymethyl methacrylate in exactly the same manner as in Example 1 except that a polycarbonate film having a thickness of 200 μm was used and polymethyl methacrylate was used instead of the composite. A molded product having a thickness of 3 mm was obtained.

The evaluation results of the obtained molded product are shown in Table 1, but were inferior in rigidity. Further, the form of destruction when the steel ball is dropped and broken is as shown in FIG. 4, and although the fragments do not scatter, large and sharp fragments are formed, and there is a high possibility that the human body will be damaged when contacted. Was something.

Comparative Example 2 A molded product having a thickness of 3 mm made of colloidal silica-dispersed resin was obtained in the same manner as in Example 1 except that no polycarbonate film was used. The obtained molded product was excellent in transparency and rigidity as shown in Table 1. However, when the steel ball was dropped and destroyed, the fragments were fine but scattered greatly around.

[0034]

[Table 1]

[0035]

The laminated molded article of the present invention has the characteristics that it is excellent in rigidity and transparency, and that small pieces when broken are not scattered, so that the occupant is injured by the broken pieces. Because it is difficult to bear, window glass of houses and vehicles,
It can be used in various fields such as various structural materials.

[Brief description of the drawings]

FIG. 1 is a photograph of a molded article of Example 1 after breaking.

FIG. 2 is a photograph of the molded article of Example 2 after breaking.

FIG. 3 is a photograph after the molded article of Example 3 is broken.

FIG. 4 is a photograph after the molded article of Comparative Example 1 was broken.

Claims (2)

[Claims] 1. A molded article obtained by laminating one or more resin films (b) on a resin substrate (a) in which colloidal silica having an average particle diameter of 50 nm or less is substantially dispersed in the form of primary particles. 2. A molding comprising a resin film (b) provided between two resin substrates (a) or between the resin substrate (a) and another type of resin substrate (c). Goods.