JP2009298954A - Flexible film or sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flexible film or sheet excellent in balance of flexibility and heat-resistance. <P>SOLUTION: The flexible film or sheet is obtained by molding a composition which is produced by compounding a thermoplastic polyurethane A, 5-50 pts.wt. of a rubber-reinforced styrenic resin (B), and 5-50 pts.wt. of a polycarbonate resin (C) having a melt flow rate (300°C, 1.2 kg load) of 10-50 g/ten minutes based on 100 pts.wt. of the thermoplastic polyurethane (A), wherein the shore A hardness of the flexible film or sheet is in the range of 60-100. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a flexible film or sheet. Specifically, the present invention relates to a flexible film or sheet excellent in flexibility and heat resistance.

Resins such as PVC, olefin, and styrene are used as materials used for flexible films or sheets in the fields of automobiles, home appliances, OA equipment, building materials, and the like. PVC-based soft materials are widely used, but there is a problem that weight loss occurs due to heating because it is necessary to add a large amount of plasticizer, and there is a possibility that dioxins may be generated during incineration. There's a problem. In addition, as a soft material other than PVC, for example, a soft material using a styrene elastomer has been proposed as a resin having a segment such as isoprene or butadiene as a soft component. However, a hard copolymer and a soft segment are block copolymers. Therefore, it is necessary to synthesize by a special non-aqueous polymerization method, and there is a disadvantage that the economy is particularly inferior in terms of equipment, productivity and the like. On the other hand, thermoplastic polyurethane is rich in wear resistance and flexibility, but has low heat resistance. Especially in film and sheet applications, when exposed to a high-temperature atmosphere in the subsequent process such as secondary processing, the film or sheet There are problems such as easy softening, the inability to maintain the shape, and the possibility of pinholes.
On the other hand, Patent Document 1 (JP-A-2-308850) and Patent Document 2 (JP-A-2-308851) propose blends of thermoplastic polyurethane and aromatic polycarbonate. Since the mixing ratio of polycarbonate is high, the flexibility specific to thermoplastic polyurethane cannot be expressed, and there is no description about a flexible film or sheet.
Japanese Patent Laid-Open No. 2-308850 JP-A-2-308851

  An object of the present invention is to provide a flexible film or sheet excellent in flexibility and heat resistance.

As a result of intensive studies in view of such problems, the present inventors have found that the above object can be achieved by mixing a specific polymer with a thermoplastic polyurethane at a specific ratio, and have reached the present invention.
That is, according to the present invention, 5 to 50 parts by weight of rubber-reinforced styrene resin (B) and melt flow rate (300 ° C., 1.2 kg load) are 10 to 50 g / 10% with respect to 100 parts by weight of thermoplastic polyurethane (A). A soft film or sheet formed by molding a composition comprising 5 to 50 parts by weight of a polycarbonate resin (C), wherein the Shore A hardness of the film or sheet is 60 to 100 A soft film or sheet is provided.

  The soft film or sheet obtained in the present invention is excellent in flexibility, wear resistance, and heat distortion resistance in a high temperature atmosphere, and therefore, such as frame processing that could not be achieved with existing soft materials. The range of use can be expanded for applications that require high temperature treatment.

Hereinafter, the present invention will be described in detail.
The soft film or sheet in the present invention is composed of 5 to 50 parts by weight of a rubber-reinforced styrene resin (B) and a melt flow rate (300 ° C., 1.2 kg load) with respect to 100 parts by weight of the thermoplastic polyurethane (A). It is obtained by molding a composition comprising 5 to 50 parts by weight of polycarbonate resin (C) that is 10 to 50 g / 10 min.

  The thermoplastic polyurethane (A) in the present invention is a polyurethane resin obtained by reacting a polyisocyanate compound (isocyanate component) and a polyhydroxyl compound (high molecular polyol and / or low molecular weight polyol).

  Examples of the polyisocyanate used in the production of the thermoplastic polyurethane (B) of the present invention include aromatic diisocyanates, alicyclic diisocyanates, and modified products of these diisocyanates. Specific examples of such diisocyanates include, for example, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, cyclohexane diisocyanate, pyridine diisocyanate, toluidine diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4. -Diphenylmethane diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 1,5-naphthylene diisocyanate and mixtures thereof.

  The polymer polyol as the polyhydroxyl compound used in the production of the thermoplastic polyurethane of the present invention is preferably a polyester polyol, a polyether polyol, a polybutadiene polyol, a polycarbonate polyol, a polyester polyether polyol or a mixture thereof.

  The polyester polyol used for the production of the thermoplastic polyurethane of the present invention includes a polyhydric alcohol and polybasic carboxylic acid condensate, a hydroxycarboxylic acid and polyhydric alcohol condensate, etc. For example, ethylene glycol, 1,2-propylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, 1,5-pentamethylene glycol, 1 , 6-hexamethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol and the like alone or as a mixture. Polybasic carboxylic acids include dibasic acids such as succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydroisophthalic acid, etc. Is exemplified. As the condensate of hydroxycarboxylic acid and polyhydric alcohol, castor oil, a reaction product such as castor oil and ethylene glycol, propylene glycol or the like can be used.

  As the low molecular polyol used in the production of the thermoplastic polyurethane of the present invention, the diol can be used.

  Furthermore, polycaprolactone diols obtained by ring-opening addition polymerization of ε-caprolactam in the presence of glycol or the like can also be used as the polyester polyol used for producing the thermoplastic polyurethane of the present invention. As these caprolactone diols, those obtained by addition polymerization of one or more of ε-caprolactam, σ-valerolactone and the like to the polyhydric alcohols described above can be used.

  As the polyether polyol used in the production of the thermoplastic polyurethane of the present invention, one or more of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran are used as compounds having two or more active hydrogens. Examples of addition-polymerized products include polyethylene glycol, polypropylene glycol, and polymethylene glycol. Examples of the compound having two or more active hydrogens include polyhydric alcohols and polybasic carboxylic acids described above, amines such as ethylenediamine and hexamethylenediamine, polyhydric phenols such as resorcin and bisphenol, Castor oil and the like.

  The polybutadiene diol used in the production of the thermoplastic polyurethane of the present invention is a diene polymer or copolymer having 4 to 12 carbon atoms having a number average molecular weight of 500 to 25000, and further, these diene monomers and 2 to 22 carbon atoms. Of olefinic addition polymer monomers, for example, polybutadiene homopolymer, polyisoprene homopolymer, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and the like.

  Polycarbonate polyols used in the production of the thermoplastic polyurethane of the present invention include polyhydric alcohols such as 1,6-hexanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol and phosgene, and chloroacetic acid. The number average molecular weight is about 300 to 15000 obtained by condensation with an ester, dialkyl carbonate or diallyl carbonate.

As the rubber-reinforced styrene resin (B) in the present invention, a styrene monomer or a styrene monomer and a vinyl cyanide monomer and other copolymer as necessary in the presence of a rubbery polymer. It is a resin obtained by copolymerization of one or more possible monomers.
The rubbery polymer that can constitute the rubber-reinforced styrene resin includes polybutadiene, polyisoprene, butadiene-styrene copolymer, isoprene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-isoprene-styrene copolymer. Polymers, diene rubbers such as polychloroprene, ethylene-propylene copolymers, ethylene-propylene rubbers such as ethylene-propylene-nonconjugated diene copolymers, ethylene-butene-1-nonconjugated diene copolymers, or Examples thereof include acrylic rubbers such as polybutyl acrylate, polyorganosiloxane rubbers, and composite rubbers composed of two or more of these rubbers. One or two or more rubbers can be used. Of these, diene rubber, ethylene-propylene rubber and acrylic rubber are particularly preferable, and acrylic rubber is most preferable.
Examples of the styrenic monomer include styrene, α-methylstyrene, paramethylstyrene, bromostyrene, and the like, and one or more of them can be used. In particular, styrene and α-methylstyrene are preferable.
Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and one or more of them can be used. Particularly preferred is acrylonitrile. Other copolymerizable monomers that can be used with styrene monomers and vinyl cyanide monomers include (meth) acrylic acid ester monomers such as methyl methacrylate and methyl acrylate. , Maleic anhydride, unsaturated acid monomers such as dimethyl maleate, and maleimide monomers such as N-phenylmaleimide and N-cyclohexylmaleimide, which are used singly or in combination. Can do.
The composition ratio of the rubber-like polymer constituting the rubber-reinforced styrene resin and the total monomer (styrene monomer, vinyl cyanide monomer and other copolymerizable monomers) is particularly limited However, from the viewpoint of the balance between the processability and physical properties of the resin composition, particularly the impact resistance, the rubber-like polymer is preferably 5 to 70% by weight and the total monomer is 95 to 30% by weight.
The rubber-reinforced styrene-based resin in the present invention can be obtained by a known emulsion polymerization method, suspension polymerization method, solution polymerization method, bulk polymerization method, or any combination thereof.
In the present invention, these rubber-reinforced styrene resins alone or rubber-reinforced styrene resins and styrene copolymer resins, polylactic acid resins, thermoplastic starch, polymethyl methacrylate resins, polyamide resins, polycarbonate resins, At least one selected from a butyl terephthalate resin, a polyethylene terephthalate resin, a polyphenylene ether resin, a polyvinyl chloride resin, a polysulfone resin, and a polyarylate resin can be mixed, and a styrene copolymer resin is particularly preferable. Of these, the styrene copolymer resin can be used for the purpose of adjusting the content concentration of the rubber-like polymer in the rubber-reinforced styrene resin. It is obtained by copolymerizing a monomer based on a vinyl cyanide monomer and, if necessary, one or more other copolymerizable monomers.

  Examples of the rubber-reinforced styrene resin (B) in the present invention include a method using a known kneader such as a Banbury mixer or an extruder when mixing the rubber-reinforced styrene resin and other thermoplastic resins. Also, there is no restriction on the mixing order, and the two components are mixed together. Furthermore, in the case of three components, not only the three components are mixed together, but also the remaining one component is mixed in advance. Is also possible.

  The polycarbonate resin (C) in the present invention is a polymer obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted, Typical examples include 2,2-bis (4-hydroxyphenyl) propane; polycarbonate resin produced from “bisphenol A”.

  Examples of the dihydroxydiaryl compound include bisphenol A, bis (4-hydroxydiphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bisbis (4-hydroxydiphenyl) phenylmethane, 2,2-bis (4-hydroxydiphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5dibromophenyl) propane, 2,2-bis (4 Bis (hydroxyaryl) alkanes such as -hydroxy-3,5-dichlorophenyl) propane; , 1-bis (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′- Dihydroxy diaryl ethers such as dihydroxy-3,3′-dimethyldiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, dihydroxy diaryl sulfides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide Dihydroxy diaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, dihydro such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Siji aryl sulfones and the like.

  These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4′-dihydroxydiphenyls, and the like may be mixed.

Further, the above-mentioned dihydroxydiaryl compound and a trivalent or higher valent phenol compound as shown below may be mixed and used. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- (4 4 '-(4,4'-hydroxydiphenyl) cyclohexyl) -propane and the like.
In addition, when manufacturing these polycarbonate resins, a molecular weight regulator, a catalyst, etc. can be used as needed.

Furthermore, in the flexible film or sheet of the present invention, in addition to the above components (A), (B) and (C), as long as the physical properties are not impaired, the resin is stable during mixing or molding depending on the purpose. Agent, UV absorber, lubricant, mold release agent, plasticizer, antistatic agent, flame retardant, pigment, dye, reinforcing agent (talc, mica, clay, glass fiber, etc.), colorant (carbon black, titanium oxide, etc.) Known additives such as inorganic fine particles (titanium oxide, silica, barium sulfate, calcium carbonate, etc.), organic cross-linked fine particles (methacrylic resin, silicon resin, etc.) can be used.
In addition, when mixing these components, the above (A), (B) and (C), as well as a method of melting and kneading other additives as needed, or melting specific two components Although the method of melt-kneading the remaining one component after kneading is mentioned, in the present invention, it is obtained by melt-kneading a predetermined amount of rubber-reinforced styrene resin (B) and polycarbonate resin (C) in advance. It is preferable that a predetermined amount of the melt-kneaded product (D) is mixed with the thermoplastic polyurethane (A) from the viewpoint of reducing deterioration of the thermoplastic polyurethane due to the compound due to heat.

Although there is no restriction | limiting in particular in the shaping | molding temperature at the time of shape | molding the multilayer film or sheet | seat of this invention, It is preferable that it is 160-200 degreeC.
The method for molding the flexible film or sheet of the present invention is not particularly limited, and for example, molding using an extruder such as roll molding, calender molding, sheet extruder, inflation molding machine, or the like was performed. It is also possible to laminate a film or sheet by adhering it to a plurality of sheets or other polymer sheets or films by an adhesive or a hot press method. Furthermore, the flexible film or sheet of the present invention may be stretched by a known uniaxial or biaxial stretching method even in an unstretched state.
The soft film or sheet thus produced can be used for vibration-proof films, sealing materials, emblems subjected to adhesive processing, and various labels. Furthermore, by using an insert molding method or an in-mold molding method using an injection molding machine or a press molding machine, it can also be used as a base film to be bonded to the surface of a thermoplastic resin such as ABS resin or polyolefin resin. is there.

〔Example〕
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not restrict | limited at all by these.

-Thermoplastic polyurethane (A-1)-
Peresen 2102-80A manufactured by Dow Chemical

-Rubber reinforced styrene resin (B)-
B-1: Based on a known emulsion polymerization method, an acrylic rubber-reinforced styrene resin (B-) is obtained from 50 parts by weight of acrylic rubber (weight average particle size: 0.1 μm), 35 parts by weight of styrene and 15 parts by weight of acrylonitrile 1) was obtained.
B-2: Acrylic rubber-reinforced styrene based on 50 parts by weight of butadiene-styrene copolymer rubber (weight average particle diameter: 0.1 μm), 35 parts by weight of styrene and 15 parts by weight of acrylonitrile based on a known emulsion polymerization method Resin (B-2) was obtained.
B-3: Based on a known emulsion polymerization method, an acrylic rubber reinforced styrene system comprising 50 parts by weight of a butadiene-styrene copolymer rubber (weight average particle size: 0.3 μm), 35 parts by weight of styrene and 15 parts by weight of acrylonitrile. Resin (B-3) was obtained.

-Polycarbonate resin (C)-
C-1: Caliber 200-30 manufactured by Sumitomo Dow (melt flow rate 30 g / 10 min, 300 ° C., 1.2 kg load)
C-2: Caliber 200-3 manufactured by Sumitomo Dow (melt flow rate 3 g / 10 min, 300 ° C., 1.2 kg load)

  The rubber-reinforced styrene resin layer (B) and the polycarbonate resin (C) were melt-kneaded with the composition shown in Table 1 to obtain melt-kneaded products (D-1 to 5).

The thermoplastic polyurethane (A), rubber-reinforced styrene resin layer (B), polycarbonate resin (C), and melt-kneaded product (D) are blended in the composition shown in Table 2, and a soft film or sheet is used under the following conditions. It was created.
[Examples 1-5, Comparative Examples 3-5]
Preparation of flexible film or sheet: An unstretched film having a thickness of 0.1 mm was prepared using a 65 mm single screw extruder with the cylinder temperature set to 200 ° C.
[Comparative Examples 1-2]
Preparation of flexible film or sheet: An unstretched film having a thickness of 0.1 mm was prepared using a 65 mm single screw extruder with the cylinder temperature set at 230 ° C.

Shore A hardness: The sheet hardness was measured in accordance with JIS K6301.
Heat resistance (flow start temperature): About 1 gram was cut out from the prepared film or sheet, dried in an oven at 100 ° C. for 2 hours, and then brought to room temperature with a desiccator as a sample. About 1 g of sample is placed in an elevated flow tester manufactured by Shimadzu Corporation, and the piston displacement (mm) when the barrel temperature is changed from 120 ° C to 200 ° C at a heating rate of 3 ° C / min under a constant load of 30 kg. ) Reached 0.2 mm, and was defined as a flow start temperature (° C.). The orifice was evaluated at L / D = 10 mm / 1 mm.

  The soft film or sheet in the present invention is excellent in flexibility and heat resistance, and is used for applications requiring high-temperature treatment such as frame treatment, anti-vibration films, sealing materials, emblems subjected to adhesive processing, and various labels. Is possible.

Claims (3)

Polycarbonate resin having 5 to 50 parts by weight of rubber-reinforced styrene resin (B) and 10 to 50 g / 10 minutes of melt flow rate (300 ° C., 1.2 kg load) with respect to 100 parts by weight of thermoplastic polyurethane (A) (C) A soft film or sheet formed by molding a composition comprising 5 to 50 parts by weight, wherein the film or sheet has a Shore A hardness of 60 to 100, or Sheet. The thermoplastic polyurethane (A) is molded by mixing a melt-kneaded product (D) obtained by previously melt-kneading the rubber-reinforced styrene resin (B) and the polycarbonate resin (C). The soft film or sheet as described. The soft film or sheet according to claim 1 or 2, wherein the rubber-reinforced styrene resin (B) is an acrylic rubber-reinforced styrene resin.