CN1950405A - Methacrylic resin composition, methacrylic resin film and chloroethylene shaped body laminated with said film - Google Patents
Methacrylic resin composition, methacrylic resin film and chloroethylene shaped body laminated with said film Download PDFInfo
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- CN1950405A CN1950405A CN 200580010265 CN200580010265A CN1950405A CN 1950405 A CN1950405 A CN 1950405A CN 200580010265 CN200580010265 CN 200580010265 CN 200580010265 A CN200580010265 A CN 200580010265A CN 1950405 A CN1950405 A CN 1950405A
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Abstract
The present invention provides a resin composition suitable for the formation of films which are excellent in transparency, weather resistance, hardness, impact resistance, resistance to fracture on bending, and moldability; and films which exhibit excellent weather resistance even when applied by lamination to moldings of plasticizer-containing PVC resin compositions. Films having the above characteristics can be made from a methacrylic resin composition (C) which is obtained by conducting the production of a methacrylate polymer (A) from a monomer mixture comprising an alkyl methacrylate as the main component by polymerization in the presence of crosslinked acrylic elastomer particles (B) obtained by copolymerizing a monomer mixture comprising an alkyl acrylate as the main component with a polyfunctional monomer having two or more nonconjugated double bonds per molecule and which is characterized by being copolymerized with 0.01 to 50 parts by weight of an ultraviolet absorber represented by the general formula (1).
Description
Technical field
The present invention relates to the metha crylic resin of ultraviolet screener performance, the based resin molded film that forms of this methacrylic acid, with the laminated occasion of the formed body of the polyvinyl chloride that contains softening agent (PVC) based resin composition system the methacrylic acid based resin film of excellent ultraviolet screener performance is arranged also, the laminated vinyl chloride formed body of this film.
Background technology
The metha crylic resin that contains the good cross-linked elastomer of the transparency, weathering resistance, hardness and shock-resistance generally can mix UV light absorber and use.Especially make the occasion that film uses, a large amount of UV light absorber of the thin more then necessary more interpolation of the thickness of film.
Therefore, the occasion of the method form film of employing extrusion moulding etc., the venting hole that produces forcing machine stops up, the problem of the hole dirt adhesion on the T font head, cooling roller albefaction etc., the occasion that needs heavy addition in addition, produce the film surface roughening, to the problem of the stripping (separating out) of film surface etc.
Even for example can in the metha crylic resin, add a large amount of UV light absorber, but because the intermiscibility of general UV light absorber and metha crylic resin is poor, it is lower molecular weight, can not bring into play ultraviolet shielding properties after the volatilization of the part of UV light absorber during extrusion moulding, in addition, owing to from the methacrylic acid based resin composition, volatilize during life-time service, thus exist the ultraviolet screener performance through the time ground reduction problem.In addition, the occasion of laminated metha crylic resin film on the formed body of the PVC based resin composition system that contains softening agent.Because the softening agent in the PVC based resin composition is impregnated in the methacrylic acid based resin film, by stripping behind the film (separating out), so promote the stripping (separating out) of methacrylic acid based resin film middle-ultraviolet lamp absorption agent.
In order to address these problems the method that the specific UV light absorber of general known selection is added.But merely add the method for specific UV light absorber, because of the film that makes because the UV light absorber stripping of being added during warm water immersion or during outdoor exposure (separating out), so can not solve the reduction of ultraviolet screener performance, or the problem of albefaction etc.
Therefore, proposed to make the method (patent documentation 1～4) that the certain monomers of metha crylic resin demonstration ultraviolet-absorbing is carried out copolymerization.Put down in writing the copolymerization of the UV light absorber of general formula (1) expression in patent documentation 1 and the patent documentation 2, but be not the polymkeric substance that contains the cross-linked elastomer particle, aspect the curved cracking of folding problem has been arranged when making the film use.Therefore, patent documentation 3 discloses the film of the polymkeric substance system that contains the cross-linked elastomer particle with patent documentation 4, but is not the polymkeric substance that can satisfy the curved cracking (resistance to fracture on bending) of folding, formability (deep processing of film) etc.
Patent documentation 1 spy opens clear 60-38411 number
Patent documentation 2 spies open flat 5-255447 number
Patent documentation 3 spies open flat 9-194542 number
Patent documentation 4 spies open flat 8-319326 number
Summary of the invention
Therefore, crave for the methacrylic acid based resin composition of the film that can form the transparency, weathering resistance, hardness, shock-resistance, the curved cracking of folding and good moldability, in addition, even laminated with the formed body of the PVC based resin composition system that contains softening agent, the methacrylic acid based resin film of weathering resistance.
The result that present inventors study with great concentration, discovery includes the acrylic ester cross-linked elastomer particle of monomer copolymerization of demonstration ultraviolet-absorbing of specific chemical structure formula and methacrylate ester polymkeric substance, the film transparency, weathering resistance, hardness and the shock-resistance that have the methacrylic acid based resin composition of specific layer structure and particle diameter to make are good, and curved cracking of folding and formability might as well, and, even be laminated on the formed body of the PVC based resin composition system that contains softening agent weathering resistance might as well, thereby finished the present invention.
That is, the present invention relates to
1. methacrylic acid based resin composition, it is characterized in that it being in the presence of acrylic ester cross-linked elastomer particle (B), to make methacrylate ester polymkeric substance (A) carry out the methacrylic acid based resin composition (C) that polymerization obtains, methacrylate ester polymkeric substance (A) carries out polymerization by the monomer mixture that contains alkyl methacrylate 50～100 weight % and alkyl acrylate 0～50 weight % and makes, acrylic ester cross-linked elastomer particle (B) is by containing the monomer mixture (b) of alkyl acrylate 50～100 weight % and alkyl methacrylate 50～0 weight %, having the multi-functional monomer of the unconjugated double bond more than 2 to carry out copolymerization with per 1 molecule makes, and with respect to methacrylic acid based resin composition (C) 100 weight parts, UV light absorber 0.01～30 weight part of copolymerization general formula (1) expression and making.
(in the formula, x is H or halogen, R
1Be H, methyl or C
4～6Tertiary alkyl, R
2Be the C of straight or branched
2～10Alkylidene group, R
3Be H or methyl.) (claim 1).
2. the described methacrylic acid based resin composition of claim 1, it is characterized in that, methacrylic acid based resin composition (C) is 2 layers of structural polymer that acrylic ester cross-linked elastomer particle (B) and methacrylate ester polymkeric substance (A) join, the median size of methacrylic acid based resin composition (C) is greater than 100nm, below the 400nm, and the content of acrylic ester cross-linked elastomer particle (B) is 5～45 weight % (claim 2).
3. with the film (claim 3) of claim 1 or 2 described methacrylic acid based resin composition (C) moulding systems.
4. with the laminate (claim 4) of the described frlml laminating of claim 2.
5. the described laminate of claim 4 (claim 5) made of injection molding.
6. with the methacrylic acid based resin film of the laminated usefulness of formed body of the polyvinyl chloride based resin composition system that contains softening agent, it is characterized in that it being in the presence of acrylic ester cross-linked elastomer particle (B), to make methacrylate ester polymkeric substance (A) carry out the methacrylic acid based resin composition (C) that polymerization obtains, methacrylate ester polymkeric substance (A) makes by making the monomer mixture that contains alkyl methacrylate 50-100 weight % and alkyl acrylate 0-50 weight % carry out polymerization, acrylic ester cross-linked elastomer particle (B) is by making the monomer mixture (b) that contains alkyl acrylate 50～100 weight % and alkyl methacrylate 50～0 weight %, having the multi-functional monomer of the unconjugated double bond more than 2 to carry out copolymerization with per 1 molecule makes, with respect to methacrylic acid based resin composition (C) 100 weight parts, UV light absorber 0.01～30 weight part of polymerization general formula (1) expression and making.
(in the formula, x is H or halogen, R
1Be H, methyl or C
4～6Tertiary alkyl, R
2Be the C of straight or branched
2～10Alkylidene group, R
3Be H or methyl.) (claim 6).
7. the methacrylic acid based resin film of the described laminated usefulness of formed body to the polyvinyl chloride based resin composition system that contains softening agent of claim 6, wherein methacrylic acid based resin composition (C) is 2 layers of structural polymer that acrylic ester cross-linked elastomer particle (B) and methacrylate ester polymkeric substance (A) join, the median size of methacrylic acid based resin composition (C) is greater than 100nm, below the 400nm, and the content of acrylic ester cross-linked elastomer particle (B) is 5～45 weight %.(claim 7)
8. the methacrylic acid based resin film of the laminated usefulness of formed body of claim 6 or 7 described and the polyvinyl chloride based resin composition systems that contain softening agent is characterized in that making the UV light absorber and the acrylic ester cross-linked elastomer particle (B) of general formula (1) expression to carry out copolymerization (claim 8).
9. the methacrylic acid based resin film of the laminated usefulness of formed body of any one of claim 6～8 is described and the polyvinyl chloride based resin composition system that contains softening agent carries out laminated pvdc layer zoarium (claim 9).
The film of the methacrylic acid based resin composition machine-shaping that the present invention is made, not only solved the problem of adding the UV light absorber generation by making the monomer that shows ultraviolet-absorbing carry out copolymerization, and it is good as the transparency, weathering resistance, hardness and the shock-resistance of film desired characteristic, and curved cracking of folding and formability might as well, even laminated with the formed body of the vinyl chloride resin composition system that contains softening agent in addition, weathering resistance might as well.
Embodiment
Methacrylate ester polymkeric substance (A) among the present invention is to make the monomer mixture that contains alkyl methacrylate 50～100 weight % and alkyl acrylate 0～50 weight % adopt the polymkeric substance of at least 1 section polymerization system.Be more preferably alkyl methacrylate 60～100 weight %, alkyl acrylate 0～40 weight %.When alkyl acrylate surpasses 50 weight %, the thermotolerance of the formed film of gained metha crylic resin combination and the tendency that hardness reduces are arranged.
Constituting the alkyl methacrylate of the methacrylate ester polymkeric substance (A) among the present invention, consider that from the viewpoint of polymerisation reactivity and cost the carbonatoms of preferred alkyl is 1～12 ester, can be that the straight chain shape also can be a chain.Concrete example as alkyl methacrylate, for example, can enumerate methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate etc., these monomers can use more than a kind or 2 kinds and use.
Constitute methacrylate ester polymkeric substance (A) among the present invention alkyl acrylate, consider that from the viewpoint of polymerisation reactivity and cost the carbonatoms of preferred alkyl is 1～12 ester, can be that the straight chain shape also can be a chain.Concrete example as alkyl acrylate, for example, can enumerate methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-EHA, vinylformic acid n-octyl etc., these monomer can use more than a kind or 2 kinds and use.
In addition, methacrylate ester polymkeric substance of the present invention (A), also can make the ethene to alkyl methacrylate and the copolymerization of alkyl acrylate energy as required is that unsaturated monomer carries out copolymerization.Ethene as these energy copolymerization is unsaturated monomer, for example, can enumerate vinylchlorid, the ethylene halide of bromine ethene etc., vinyl cyanide, the vinyl cyanide of methacrylonitrile etc., vinyl formate, vinyl-acetic ester, the vinyl ester of propionate etc., vinylbenzene, Vinyl toluene, the aromatic vinyl radical derivative of alpha-methyl styrene etc., vinylidene chloride, the vinylidene halide of vinylidene etc., vinylformic acid, sodium acrylate, vinylformic acid and salt thereof such as calcium acrylate, propenoic acid beta-hydroxy ethyl ester, the vinylformic acid dimethylamino ethyl ester, glycidyl acrylate, acrylamide, the acrylic acid alkyl ester derivative of N hydroxymethyl acrylamide etc., methacrylic acid, sodium methacrylate, the methacrylic acid and the salt thereof of methacrylic acid calcium etc., Methacrylamide, Jia Jibingxisuanβ-Qiang Yizhi, dimethylaminoethyl acrylate methyl base ammonia ethyl ester, the alkyl methacrylate derivatives of glycidyl methacrylate etc. etc., these monomers can more than 2 kinds and be used.
The acrylic ester cross-linked elastomer particle (B) that uses among the present invention is that the mixture that makes the monomer mixture (b) that contains alkyl acrylate 50～100 weight % and alkyl methacrylate 50～0 weight %, has the polyfunctional monomer of the unconjugated double bond more than 2 to make with per 1 molecule adopts the cross-linked elastomer particle that copolymerization forms more than at least 1 section.Monomer mixture (b) is more preferably alkyl acrylate 60～100 weight % and alkyl methacrylate 40～0 weight %.When alkyl methacrylate surpasses 50 weight %, the tendency of the curved cracking reduction of folding of the film that is formed by gained methacrylic acid based resin composition is arranged.
In addition, in the acrylic ester cross-linked elastomer particle of the present invention (B), also can as required and can be that unsaturated monomer carries out copolymerization with the ethene of alkyl methacrylate and alkyl acrylate copolymer.
Acrylic ester cross-linked elastomer particle (B) among the present invention, owing to have the multi-functional monomer of the unconjugated reactive double bond more than 2 to carry out copolymerization with per 1 molecule, the polymkeric substance that makes shows cross-linking elasticity.In addition, do not react during acrylic ester cross-linked elastomer particle (B) polymerization and a residual reactive functional group (two key) becomes the grafting point of crossing, make a certain proportion of methacrylate ester multipolymer (A) and acrylic ester cross-linked elastomer particle (B) carry out grafting.Therefore acrylic ester cross-linked elastomer particle (B) is discontinuous and be evenly dispersed in the methacrylate ester multipolymer (A).
As the multi-functional monomer that uses among the present invention, can enumerate allyl methacrylate(AMA), allyl acrylate, triallyl cyanurate, triallyl isocyanurate, Phthalic acid, diallyl ester, diallyl maleate, hexanodioic acid divinyl ester, dimethacrylate Vinylstyrene glycol ester, diacrylate Vinylstyrene glycol ester, diethyleneglycol dimethacrylate(DEGDMA), the diacrylate binaryglycol ester, the dimethacrylate triglycol ester, the diacrylate triglycol ester, trimethylolpropane trimethacrylate, Viscoat 295, tetramethylol methane tetramethyl-acrylate, tetrapropylene acid tetramethylol methane ester, dipropyleneglycol dimethacrylate and dipropylene glycol diacrylate etc., these can more than 2 kinds and be used.
Multi-functional monomeric addition in the acrylic ester cross-linked elastomer particle of the present invention (B) is with respect to aforementioned monomer mixture (b) 100 weight parts, preferred 0.05～20 weight part, more preferably 0.1～10 weight part.Multi-functional monomeric addition is during less than 0.05 weight part, the shock-resistance of the film that is formed by the methacrylic acid based resin composition and the tendency that the curved cracking of folding reduces are arranged, when surpassing 20 weight parts, the tendency that also has the curved cracking of shock-resistance and folding to reduce.
The ethene of employed alkyl acrylate, alkyl methacrylate and energy and these monomer copolymerizations is the concrete example of unsaturated monomer in the acrylic ester cross-linked elastomer particle of the present invention (B), can enumerate the concrete example that uses in the aforementioned methacrylate ester polymkeric substance (A).
The methacrylic acid based resin composition (C) that uses among the present invention is to make methacrylate ester polymkeric substance (A) carry out the multilayer structure polymer that polymerization makes in the presence of acrylic ester cross-linked elastomer particle (B).
Wherein, as the methacrylic acid based resin composition (C) that uses among the present invention, consider from the curved cracking of folding and the viewpoint of formability (deep processing of film), preferably 2 layers of structural polymer joining of acrylic ester cross-linked elastomer particle (B) and methacrylate ester polymkeric substance.With respect to this, for example, methacrylate ester polymkeric substance (A), acrylic ester cross-linked elastomer particle (B) carry out this 3-tier architecture polymkeric substance of polymeric with methacrylate ester multipolymer (A) sequential stages ground again, and the tendency of the curved cracking reduction of folding of the film that is formed by gained methacrylic acid based resin composition is arranged.
The content of the acrylic ester cross-linked elastomer particle (B) among the present invention all is the occasion of 100 weight % with methacrylic acid based resin composition (C), preferred 5～45 weight %, more preferably 10～40 weight %, preferred again 15～35 weight %.The content of acrylic ester cross-linked elastomer particle (B) is during less than 5 weight %, the shock-resistance of the film that is formed by gained methacrylic acid based resin composition and the tendency that the curved cracking of folding reduces are arranged, when surpassing 45 weight %, there are the hardness of film and the tendency that formability reduces.
The methacrylic acid based resin composition (C) that uses among the present invention is the methacrylic acid based resin composition that the UV light absorber copolymerization with general formula (1) expression forms.
General formula (1)
(in the formula, x is H or halogen, R
1Be H, methyl or C
4～6Tertiary alkyl, R
2Be the C of straight or branched
2～10Alkylidene group, R
3Be H or methyl.)
UV light absorber as formula of of the present invention (1) expression, particularly, for example be 2-(2 '-hydroxyl-5 '-the methacryloxyethyl phenyl)-the 2H-benzotriazole category, can enumerate 2-(2 '-hydroxyl-5 '-the acryloxy ethylphenyl)-the 2H-benzotriazole, 2-(2 '-hydroxyl-5 '-the methacryloxyethyl phenyl)-the 2H-benzotriazole, 2-(2 '-hydroxyl-5 '-the methacryloxyethyl phenyl)-5-chloro-2H-benzotriazole, 2-(2 '-hydroxyl-5 '-the methacryloxypropyl phenyl)-the 2H-benzotriazole, 2-(2 '-hydroxyl-5 '-methacryloxyethyl-3 '-tert-butyl-phenyl)-the 2H-benzotriazole etc.Wherein, from cost and operability consider to be more preferably 2-(2 '-hydroxyl-5 '-the methacryloxyethyl phenyl)-the 2H-benzotriazole.
The copolymerization ratio of the UV light absorber of formula of of the present invention (1) expression, with respect to methacrylic acid based resin composition (C) 100 weight parts, preferred 0.01～30 weight part, more preferably 0.01～25 weight part, preferred 0.01～20 weight part, special preferred 0.05～20 weight part again.The copolymerization ratio of the UV light absorber of general formula (1) expression is during less than 0.01 weight part, the tendency that the film that existence is formed by gained methacrylic acid based resin composition and the weathering resistance of vinyl chloride-based resin laminating film reduce, when surpassing 50 weight parts, there are the shock-resistance of film and the tendency that the curved cracking of folding reduces.
The copolymerization of the UV light absorber of formula of of the present invention (1) expression, also can carry out copolymerization at any one deck of methacrylic acid based resin composition (C), consider from the viewpoint of the weathering resistance of film, preferred methacrylate ester multipolymer (A) not only, and carry out copolymerization with acrylic ester cross-linked elastomer particle (B), consider that from the viewpoint of the weathering resistance of film more preferably UV light absorber and methacrylic acid based resin composition (C) all carry out copolymerization equably.
The manufacture method of the methacrylic acid based resin composition (C) among the present invention does not have particular determination, can use known emulsion polymerization, emulsion-suspension polymerization, suspension polymerization, mass polymerization or solution polymerization process, special preferred emulsion polymerization.
The copolymerization process of the UV light absorber of the general formula among the present invention (1) expression does not have particular determination yet.Preferably in the manufacturing of methacrylic acid based resin composition (C), carry out copolymerization.As copolymerization process, can use known emulsion polymerization, emulsion-suspension polymerization, suspension polymerization, mass polymerization or solution polymerization process, special preferred emulsion polymerization.
As the initiator in the polymerization of acrylic ester cross-linked elastomer particle of the present invention (B), can use known organic system superoxide, inorganic be the initiator of superoxide, azo-compound etc.Particularly, for example can use t-butyl hydroperoxide, peroxidation 1,1,3, the 3-tetramethyl butyl, the organo-peroxide of succinic acid peroxide, the peroxidation toxilic acid tert-butyl ester, hydrogen phosphide cumene, benzoyl peroxide etc., or the inorganic peroxide of Potassium Persulphate, Sodium Persulfate etc. can also use the oil-soluble initiator of Diisopropyl azodicarboxylate etc.These may be used alone, two or more kinds can also be used.These initiators also can be used as the common oxidation-reduction type initiator that the reductive agent of the complex compound of S-WAT, Sulfothiorine, formaldehyde sodium sulfoxylate, xitix, hydroxyl acetonic acid, ferrous sulfate, ferrous sulfate and disodium ethylene diamine tetraacetate etc. combines and use.
Aforementioned organic system superoxide can adopt the method for directly adding in the polymerization system, be blended in the method for adding in the monomer, being dispersed in the known additive processs such as method of adding in the emulsifier aqueous solution adds, but consider from the viewpoint of the transparency, preferably be blended in the method for adding in the monomer or be dispersed in the method for adding in the emulsifier aqueous solution.
In addition, aforementioned organic system superoxide, consider that from the viewpoint of polymerization stability, particle diameter control preferably the redox series initiators that combines as the organic system reductive agent of the inorganic reducing agent of the molysite of divalent etc. and/or formaldehyde sodium sulfoxylate, reducing sugar, xitix etc. uses.
The tensio-active agent that aforementioned letex polymerization is used does not have particular determination, the tensio-active agent that can use common letex polymerization to use.Particularly, for example can enumerate the anionic surfactant of alkyl sodium sulfonate, sodium alkyl benzene sulfonate, dioctyl sodium sulphosuccinate, Sodium Lauryl Sulphate BP/USP, sodium soap etc., or the nonionic surfactant of the resultant of reaction of induced by alkyl hydroxybenzene, aliphatics alcohols and propylene oxide, oxyethane etc. etc.These tensio-active agent may be used alone, two or more kinds can also be used.Can also use the cationic surfactant of alkylamine salt etc. as required.
The median size of methacrylic acid based resin composition (C) latex that the present invention makes be preferably greater than 100nm, 400nm following, more preferably greater than 100nm, below the 350nm, again be preferably greater than 100nm, below the 300nm.The median size of methacrylic acid based resin composition (C) latex is when 100nm is following, the tendency that the curved cracking of the shock-resistance of the film that existence can be formed by gained methacrylic acid based resin composition and folding reduces, the tendency that exists the transparency of film to reduce when surpassing 400nm.
Methacrylic acid based resin composition (C) latex that makes, adopt common solidify, washing and exsiccant operation, or the processing by spraying drying, lyophilize etc. separates, reclaims resin combination.
The methacrylic acid based resin composition (C) that the present invention makes, can adopt the various plastic working methods of injection molding, extrusion moulding, blow molding, compressed moulding etc. to be processed into various moulded products.
Methacrylic acid based resin composition of the present invention (C), be particularly suitable for making film and use, for example, adopt inflation film process or T font head extrusion molding as common extrusion by melting, perhaps rolling process also can adopt solvent casting method etc. to process well.In addition, can also when forming film, contact with cylinder or metal strip as required by side by side making the film two sides, particularly by side by side be heated to second-order transition temperature more than the cylinder or the metal strip of temperature contact, can obtain the better film of superficiality.In addition, according to purpose, can also be by the laminated moulding of film, the biaxial stretch-formed deep processing of carrying out film.
In addition, in the methacrylic acid based resin composition of the present invention (C), can also cooperate poly-glutarimide, Pyroglutaric acid polymkeric substance, lactone cyclisation metha crylic resin, metha crylic resin, pet resin, polybutylene terephthalate resin, polyvinylidene fluoride resin etc. as required.The method of blending does not have particular determination, can adopt known method.
In the methacrylic acid based resin composition of the present invention (C), can add inorganic series pigments or organic system dyestuff for painted, can add oxidation inhibitor, thermo-stabilizer, UV light absorber, ultra-violet stabilizer etc. in order further to improve to the stability of heat or light, or add antiseptic-germicide, reodorant, lubricant, these can add separately, also can make up interpolation more than 2 kinds.
Preferred 10～300 μ m of thickness of the film that makes by methacrylic acid based resin composition of the present invention (C), more preferably 10～200 μ m.The thickness of film is during less than 10 μ m, the tendency that has the processibility of film to reduce, and when surpassing 300 μ m, the tendency that has the transparency of the film that makes to reduce.
In addition, by the film that methacrylic acid based resin composition of the present invention (C) makes, can also adopt known method to reduce the gloss of film surface as required.For example, can adopt methacrylic acid based resin composition (C) and inorganic filler or bridging property polymer particle are carried out mixing enforcements such as method.In addition, also can be by the film that makes being carried out the gloss of embossing processing reduction film surface.
The film that is made by methacrylic acid based resin composition of the present invention can be laminated in upward use such as metal, plastics.As the laminated method of film, can enumerate laminated moulding, or behind coating adhesive on the metal sheet of steel plate etc., on metal sheet, place the laminated method of wet type, the laminated method of dry type that the film after drying fits, extruding layer is legal, hot melt layer is legal etc.
Method as laminate film on plastics, can enumerate in advance film is configured in the mould, adopt the embedding moulding or the laminated injection extrusion forming of injection molding potting resin, be configured in the mould after perhaps being pre-formed film, adopt the embedding moulding of injection molding potting resin etc.
The film laminates that is made by methacrylic acid based resin composition of the present invention can replace the aspects such as cover, electric or electron device part of office equipment of cover, facsimile recorder etc. of building component, daily use Sundry goods, furniture or electrical equipment of the purposes, window frame, bathroom fittings, wallpaper, earth material etc. of application to use at automobile interior trim material, automobile decorative material etc.In addition, as moulded products, can use with the aspects such as shell, toy or recreation product of film, the necessary medical treatment product of germicidal treatment, microwave oven, tame electrical article with light guiding plate, liquid crystal with mirror, automobile headlamp, optical lens, fiber optics, CD, liquid crystal in illumination.
Can be laminated in the formed body of the vinyl chloride resin composition system that contains softening agent by the film of methacrylic acid based resin composition system of the present invention, for example, sheet material, extrusion molding article etc. are gone up and are used.
By frlml laminating that methacrylic acid based resin composition of the present invention is made to the formed body of the vinyl chloride resin composition system that contains softening agent, can prevent because of softening agent to the methacrylic acid based resin film soak into or the promoted methacrylic acid based resin film of stripping (separating out) in the stripping (separating out) of UV light absorber.
As the method for the frlml laminating that methacrylic acid based resin composition of the present invention is made to the formed body of the vinyl chloride resin composition system that contains softening agent, can enumerate laminated moulding or behind coating adhesive on vinylchlorid sheet material, the moulded products etc., place on vinyl chloride sheet material, moulded products etc. that the wet type that film drying fits is laminated, dry type is laminated, extrusion laminate, hot melt are laminated etc.
Method as laminate film on the parts of the vinyl chloride resin composition system that contains softening agent, can enumerate in advance film is configured in the mould, adopt the embedding moulding or the laminated injection extrusion forming of injection molding potting resin, be configured in the mould after perhaps being pre-formed film, adopt the embedding moulding of injection molding potting resin etc.
The vinyl chloride resin composition that contains softening agent among the present invention does not have particular determination, preferably mixes the composition of the flexible vinyl chloride resin formation of dioctyl phthalate (DOP) (DOP), dibutyl phthalate (DBP), Octyl adipate (DOA), dioctyl sebacate softening agent such as (DOS) in vinyl chloride-based resin.
Vinyl chloride-based resin among the present invention is not only ryuron, also comprises other monomeric multipolymer of vinylchlorid and vinyl acetate etc., the chlorinated vinyl chloride resin of post chlorization.In addition, also comprise the flexible vinyl chloride resin is carried out coating, dipping or laminated resin.
Methacrylic acid based resin film of the present invention and the laminate that contains the vinyl chloride-based resin formed body of softening agent, can be at automobile interior trim, automobile such as decorates outward at the purposes that replaces application, the construction of window frame, bathroom fittings, wallpaper, earth material etc., aspects such as the cover of the office equipment of the cover of daily use Sundry goods, furniture or electrical equipment, facsimile recorder etc., electric or electron device part are used.
Embodiment
Below, according to embodiment the present invention is described in more detail, but the present invention is not subjected to any qualification of these embodiment.
Each measuring method of the rerum natura of measuring in following embodiment and the comparative example is as follows.
(evaluation of polymerisation conversion)
Methacrylic acid based resin composition (C) latex that makes 120 ℃ of following dryings in hot air dryer were asked the solids component amount in 1 hour, calculated polymerisation conversion (%) by 100 * solids component amount/adding monomer (%).
(evaluation of latex median size)
The emulsion that methacrylic acid based resin composition (C) latex that makes is diluted to solid component concentration 0.02% uses spectrophotometer (HITACHI system, spectrophotometer U-2000) to obtain median size by the light penetration under the wavelength 546nm as test portion.
(evaluation of the transparency)
The transparency of the film that makes is pressed JIS K6714, measures mist degree under the condition of 23 ℃ ± 2 ℃ of temperature and humidity 50% ± 5%.
(evaluation of pencil hardness)
The plumbous benzene hardness of the film that makes is measured by JIS S-1005.
(evaluation of the curved cracking of folding)
With 1 bending of film, 180 degree that make, the variation of pressing n=5 visual valuation bending part.
Zero: not be full of cracks
△: or be with or without be full of cracks
*: be full of cracks fully
(evaluation of formability)
Carried out film forming in continuous 3 hours, observe the moulding operational situation, estimate by following standard.
Zero: the thickness of film is even, and the ground moulding of can not rupturing.
△: uneven film thickness is spared or film ruptures.
*: the film fracture, take place in film in uneven thickness.
(evaluation of the UV light absorber property separated out)
Carry out 3 hours film formings continuously, observe adhesion situation, estimate by following standard to cooling roller.
Zero: do not adhere to cooling roller.
*: adhere to cooling roller.
(evaluation of ultraviolet radiation absorption energy conservation rate)
According to following making flexible vinyl chloride resin sheet.Promptly, in vinyl chloride resin (clock deep pool chemical industry system, S1003) in 100 parts, adding is as 40 parts of the DOP of softening agent, 0.5 part (reason is ground PVC ミ Application system with the ester base lubricant as the higher alcohols of lubricant (flower king system, カ Le ュ one Le 86), pH18) 0.5 part, octyl group Sn is that (day east changes into system to stablizer, TV S8813) 0.4 part with (TVS 8831, changing into system of day east) 1 part carry out the powder mixing after, use roller/pressurization to process that (LABORATORY MILL (KANSAI ROLL corporate system) carried out roller mixing 5 minutes under 180 ℃ of roll temperatures.Use oil pressure press (refreshing rattan metal industry institute corporate system, シ Application ト one F type), at 185 ℃ of temperature and 10kg/cm
2Add depress will make mixing thing compacting 10 minutes, make the thick test of 1mm flexible vinyl chloride resin sheet.
With the film that makes and above-mentioned flexible vinyl chloride resin sheet at 180 ℃ of laminated temperatures and 50kg/cm
2Pressurization compacting down made laminated in 3 minutes.
70 ℃ of heating after 1 month down, use UV spectrograph (Hitachi's system, automatic spectrophotometer U-3210 type) to measure the following UV shielding rate (=1-UV transmitance) of wavelength 360nm, adopt following formula to calculate tight outer line absorption energy conservation rate (%) laminated of making.
Ultraviolet radiation absorption energy conservation rate (%)=100 * (the UV shielding rate after the heating)/(the UV shielding rate before the heating) (%)
In addition, " part " expression weight part in Production Example, embodiment and the comparative example, " % " expression weight %.In addition, dummy suffix notation is represented following material respectively.
BA: butyl acrylate
MMA: methyl methacrylate
CHP: hydrogen phosphide cumene
TDM: uncle's lauryl mercaptan
A1MA: allyl methacrylate(AMA)
RUVA:2-(2 '-hydroxyl-5 '-the methacryloxyethyl phenyl)-2-H-benzotriazole (the chemical company limited of big system, RUVA-93).
The manufacturing of (Production Example 1) methacrylic acid based resin composition
Material below in the 8L poly-unit of band stirrer, adding.
200 parts of deionized waters
0.25 part of dioctyl sodium sulphosuccinate
0.15 part of formaldehyde sodium sulfoxylate
0.001 part of ethylenediamine tetraacetic acid (EDTA)-2-sodium
0.00025 part in ferrous sulfate
Use nitrogen with after replacing fully in the polymeric kettle, in fact becoming the state of anaerobic, interior temperature rise to 60 ℃, the monomer mixture (B) that adds (1) in the table 1 expression continuously in 10 parts/hour ratios (promptly, 100 parts of the monomer mixtures of forming with respect to BA90% and MMA10%, contain 1 part of A1MA and 0.2 part of CHP 30 parts of monomer mixtures, and 0.6 part of RUVA), after adding end, continued again polymerase 10 .5 hour, make acrylic ester cross-linked elastomer particle (B).Polymerisation conversion is 99.5%.
Then, behind 0.05 part of the adding dioctyl sodium sulphosuccinate, interior temperature rise to 60 ℃, the monomer mixture (A) that adds (1) in the table 1 expression continuously in 10 parts/hour ratios (promptly, 100 parts of the monomer mixtures of forming with respect to BA 10% and MMA 90%, contain 0.5 part of tDM and 0.5 part of composition of CHP 70 parts of monomer mixtures, and 1.4 parts of RUVA), continued polymerization again 1 hour, make methacrylic acid based resin composition (C).Polymerisation conversion is 98.5%.Use calcium chloride with the latex that makes saltout, solidify, washing, drying, obtain toner (1).Re-using φ 40mm exhaust single screw extrusion machine is set in 240 ℃ to barrel temperature and carries out melting mixing, granulation.
Table 1
| Methacrylic acid based resin composition (C) | |||||||||||||
| (1) | (2) | (3) | (4) | (5) | (6) | (7) | (8) | (9) | (10) | (11) | (12) | ||
| Initial stage dioctyl sodium sulphosuccinate amount | (part) | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.2 | 0.4 | 0.1 |
| Acrylic ester cross-linked elastomer particle (B) | Weight part | 30 | 15 | 20 | 30 | 30 | 30 | 30 | 30 | 50 | 30 | 30 | 30 |
| BA(％) | 90 | 100 | 90 | 90 | 90 | 90 | 90 | 10 | 90 | 90 | 90 | 90 | |
| MMA(％) | 10 | 0 | 10 | 10 | 10 | 10 | 10 | 90 | 10 | 10 | 10 | 10 | |
| AIMA (part) | 1 | 2 | 3 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | |
| CHP (part) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.5 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | |
| RUVA (part) | 0.6 | 1 | 0.4 | 0.03 | 0 | 10.5 | 0.6 | 0.6 | 1 | 0.6 | 0.6 | 0.6 | |
| Methacrylate ester polymkeric substance (A) | Weight part | 70 | 85 | 80 | 70 | 70 | 70 | 70 | 70 | 50 | 70 | 70 | 70 |
| BA(％) | 10 | 10 | 10 | 10 | 10 | 10 | 80 | 10 | 10 | 10 | 10 | 10 | |
| MMA(％) | 90 | 90 | 90 | 90 | 90 | 90 | 20 | 90 | 90 | 90 | 90 | 90 | |
| TDM (part) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.4 | 0.5 | 0.5 | |
| CHP (part) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 1 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | |
| RUVA (part) | 1.4 | 4 | 1.6 | 0.07 | 0 | 24.5 | 1.4 | 1.4 | 1 | 1.4 | 1.4 | 1.4 | |
(Production Example 2-9)
Except as table 1, changing monomer forms, similarly carry out polymerization with Production Example 1, solidify, make toner (2)-(9) after the washing, drying, carry out melting mixing, granulation again.But Production Example (6) is carried out emulsion condensation in the polymerization process, thus can not obtain toner (6), can not granulation and filming, can not estimate the film rerum natura.
In addition, Production Example (5), with respect to toner (5) 100 weight parts that make, blending as 2 parts of the TinnvinP (the vapour Bart plants chemical company system) of the structural formula (2) of UV light absorber expression after, carry out melting mixing, granulation.
(Production Example 10-12)
Except the dioctyl sodium sulphosuccinate and monomer composition that as table 1, change initial adding, similarly carry out polymerization with Production Example 1, by changing the amount of dioctyl sodium sulphosuccinate, obtained changing the resin of latex median size, solidify, after the washing, drying, obtain toner (10)-(12), carry out melting mixing, granulation again.
(Production Example 13)
Before the polymerization of adding 20 parts of monomer mixtures containing 1 part of A1MA and 0.2 part of CHP and the acrylic ester cross-linked elastomer particle (B) of 0.4 part of RUVA in 100 parts of ratios of monomer mixture (b) of forming with respect to BA90% and MMA10% continuously in 10 minutes/hour, carry out 100 parts of the monomer mixtures (b ') formed with respect to BA10% and MMA90% earlier, add continuously in 10 parts/hour ratios beyond the polymerization of 10 parts of monomer mixtures containing 1 part of A1MA and 0.2 part of CHP and the methacrylate ester multipolymer (A ') of 0.2 part of RUVA, similarly carry out polymerization with Production Example 1, solidify, washing, drying makes toner (9), carry out melting mixing, granulation again.
(embodiment 1-9, comparative example 1-4)
Use band T font head φ 40mm forcing machine, the pellet that under 240 ℃ of head temperatures Production Example is made carries out moulding, makes the film of thick 100 μ m.
The kind specific character of having used the film that makes is estimated, evaluation result is shown in table 2.
Table 2
| Embodiment | Comparative example | ||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 1 | 2 | 3 | 4 | |
| Methacrylic acid based resin composition (C) | (1) | (2) | (3) | (4) | (9) | (10) | (11) | (12) | (13) | (5) | (6) | (7) | (8) |
| Polymerisation conversion (%) | 98.5 | 98.7 | 98.5 | 99 | 98.1 | 98.6 | 98.2 | 98.4 | 98.5 | 98.9 | 85.3 | 97.8 | 98.3 |
| Median size () | 1520 | 1650 | 1230 | 1540 | 1540 | 2070 | 920 | 4200 | 1500 | 1510 | Cohesion *) | 1520 | 1470 |
| The transparency (%) | 0.5 | 0.6 | 0.6 | 0.6 | 0.8 | 0.6 | 0.4 | 2.2 | 0.6 | 0.5 | - *) | 0.6 | 0.6 |
| Pencil hardness | B | H | H | B | 3B | B | B | B | B | B | - *) | 6B | H |
| Anti-crooked cracking | ○ | ○ | ○ | ○ | ○ | ○ | △ | ○ | △ | ○ | - *) | ○ | × |
| Formability | ○ | ○ | ○ | ○ | △ | ○ | △ | ○ | ○ | ○ | - *) | × | × |
| The property separated out | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | - *) | ○ | ○ |
*) Production Example (6) is because emulsion condensation during letex polymerization, so can not make resin powder (6), can not make film.
Embodiment 10～18, comparative example 5～8
Use band T font head φ 40mm forcing machine, the pellet that under 240 ℃ of head temperatures Production Example is made carries out moulding, makes the film of thick 100 μ m.
Re-use the evaluation that the film that makes carries out ultraviolet radiation absorption energy conservation rate, evaluation result is shown in table 3.
Table 3
| Embodiment | Comparative example | ||||||||||||
| 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 5 | 6 | 7 | 8 | |
| Methacrylic acid based resin composition (C) | (1) | (2) | (3) | (4) | (9) | (10) | (11) | (12) | (13) | (5) | (6) | (7) | (8) |
| Polymerisation conversion (%) | 98.5 | 98.7 | 98.5 | 99 | 98.1 | 98.6 | 98.2 | 98.4 | 98.5 | 98.9 | 85.3 | 97.8 | 98.3 |
| Median size () | 1520 | 1650 | 1230 | 1540 | 1540 | 2070 | 920 | 4200 | 1500 | 1510 | Cohesion *) | 1520 | 1470 |
| The transparency (%) | 0.5 | 0.6 | 0.6 | 0.6 | 0.8 | 0.6 | 0.4 | 2.2 | 0.6 | 0.5 | - *) | 0.6 | 0.6 |
| Pencil hardness | B | H | H | B | 3B | B | B | B | B | B | - *) | 6B | H |
| Anti-crooked cracking | ○ | ○ | ○ | ○ | ○ | ○ | △ | ○ | △ | ○ | - *) | ○ | × |
| Formability | ○ | ○ | ○ | ○ | △ | ○ | △ | ○ | ○ | ○ | - *) | × | × |
| Ultraviolet radiation absorption can conservation rate (%) | 98 | 97 | 98 | 99 | 97 | 95 | 98 | 97 | 98 | 56 | - *) | 97 | 98 |
Emulsion condensation when * Production Example (6) is owing to letex polymerization so can not make resin powder (6), can not be made film.
When the content of the monomer ratio of components of methacrylic acid based resin composition (C), layer structure, median size and acrylic ester cross-linked elastomer particle (B) does not depart from the scope of the present invention, can make the transparency, weathering resistance, hardness, shock-resistance, the curved cracking of folding and the good film of moulding.
Claims (9)
1. methacrylic acid based resin composition, it is characterized in that it being in the presence of acrylic ester cross-linked elastomer particle (B), to make methacrylate ester polymkeric substance (A) carry out the methacrylic acid based resin composition (C) that polymerization makes, methacrylate ester polymkeric substance (A) makes by making the monomer mixture that contains alkyl methacrylate 50-100 weight % and alkyl acrylate 0-50 weight % carry out polymerization, acrylic ester cross-linked elastomer particle (B) is by making the monomer mixture (b) that contains alkyl acrylate 50-100 weight % and alkyl methacrylate 50-0 weight %, having the multi-functional monomer of the unconjugated double bond more than 2 to carry out copolymerization with per 1 molecule makes, and with respect to methacrylic acid based resin composition (C) 100 weight parts, the UV light absorber 0.01-30 weight part of copolymerization general formula (1) expression makes
General formula (1)
In the formula, X is H or halogen, R
1Be H, methyl or C
4-6Tertiary alkyl, R
2Be the C of straight or branched
2-10Alkylidene group, R
3Be H or methyl.
2. the described methacrylic acid based resin composition of claim 1 (C), it is characterized in that methacrylic acid based resin composition (C) is 2 layers of structural polymer that acrylic ester cross-linked elastomer particle (B) and methacrylate ester polymkeric substance (A) join, the median size of methacrylic acid based resin composition (C) is greater than 100nm, below the 400nm, and the content of acrylic ester cross-linked elastomer particle (B) is 5-45 weight %.
3. the film that claim 1 or 2 described methacrylic acid based resin composition (C) moulding are made.
4. the laminate that the described frlml laminating of claim 3 is formed.
5. adopt the described laminate of claim 4 of injection molding manufacturing.
6. with the methacrylic acid based resin film of the laminated usefulness of formed body of the polyvinyl chloride based resin composition system that contains softening agent, it is characterized in that it being in the presence of acrylic ester cross-linked elastomer particle (B), to make methacrylate ester polymkeric substance (A) carry out the methacrylic acid based resin composition (C) that polymerization makes, methacrylate ester polymkeric substance (A) makes by making the monomer mixture that contains alkyl methacrylate 50-100 weight % and alkyl acrylate 0-50 weight % carry out polymerization, acrylic ester cross-linked elastomer particle (B) is by making the monomer mixture (b) that contains alkyl acrylate 50-100 weight % and alkyl methacrylate 50-0 weight %, having the multi-functional monomer of the unconjugated double bond more than 2 to carry out copolymerization with per 1 molecule makes, and with respect to methacrylic acid based resin composition (C) 100 weight parts, carry out copolymerization with the UV light absorber 0.01-30 weight part of general formula (1) expression and make the methacrylic acid based resin composition
In the formula, X is H or halogen, R
1Be H, methyl or C
4-6Tertiary alkyl, R
2Be the C of straight or branched
2-10Alkylidene group, R
3Be H or methyl.
7. the described methacrylic acid based resin film of the laminated usefulness of formed body with the polyvinyl chloride based resin composition system that contains softening agent of claim 6, it is characterized in that methacrylic acid based resin composition (C) is 2 layers of structural polymer that acrylic ester cross-linked elastomer particle (B) and methacrylate ester polymkeric substance (A) join, the median size of methacrylic acid based resin composition (C) is greater than 100nm, below the 400nm, and the content of acrylic ester cross-linked elastomer particle (B) is 5-45 weight %.
8. the methacrylic acid based resin film of the laminated usefulness of formed body of claim 6 or 7 described and the polyvinyl chloride based resin composition systems that contain softening agent is characterized in that making the UV light absorber and the acrylic ester cross-linked elastomer particle (B) of general formula (1) expression to carry out copolymerization.
9. the vinyl chloride laminate that the methacrylic acid based resin film of the laminated usefulness of formed body of any one of claim 6-8 is described and the polyvinyl chloride based resin composition system that contains softening agent carries out laminated.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102056984B (en) * | 2008-06-10 | 2014-07-16 | 株式会社钟化 | Fluororesin film and fluororesin-laminated acrylic resin film |
| CN104220930A (en) * | 2012-04-03 | 2014-12-17 | 斯坦雷电气株式会社 | Strobe light device |
| CN106062072A (en) * | 2014-03-07 | 2016-10-26 | 株式会社钟化 | Methacrylic resin composition |
| CN107109018A (en) * | 2014-11-19 | 2017-08-29 | 株式会社可乐丽 | Acrylic films |
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2005
- 2005-03-28 CN CNB2005800102659A patent/CN100482703C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102056984B (en) * | 2008-06-10 | 2014-07-16 | 株式会社钟化 | Fluororesin film and fluororesin-laminated acrylic resin film |
| CN104220930A (en) * | 2012-04-03 | 2014-12-17 | 斯坦雷电气株式会社 | Strobe light device |
| CN106062072A (en) * | 2014-03-07 | 2016-10-26 | 株式会社钟化 | Methacrylic resin composition |
| CN106062072B (en) * | 2014-03-07 | 2019-06-07 | 株式会社钟化 | Methacrylic resin composition |
| CN107109018A (en) * | 2014-11-19 | 2017-08-29 | 株式会社可乐丽 | Acrylic films |
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