CN102167942A - Primer for plastic with inorganic film, plastic with inorganic film, decorative film for inner mold forming and decorative film for insert part forming - Google Patents
Primer for plastic with inorganic film, plastic with inorganic film, decorative film for inner mold forming and decorative film for insert part forming Download PDFInfo
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- CN102167942A CN102167942A CN2011100481258A CN201110048125A CN102167942A CN 102167942 A CN102167942 A CN 102167942A CN 2011100481258 A CN2011100481258 A CN 2011100481258A CN 201110048125 A CN201110048125 A CN 201110048125A CN 102167942 A CN102167942 A CN 102167942A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
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Abstract
The invention provides a novel primer for producing a plastic with an inorganic film, which is closely connected to the inorganic film and a plastic substrate, and will not generate cracks that can be seen by eyes, interference fringes and obvious whitening parts on the inorganic film even the plastic with inorganic film is processed under high temperature. The primer uses an acrylic acid copolymer (A) having carboxylate anion group with a vitrification temperature of minus 5-120 DEG and a polyaziridine compound (B) having at least three aziridinyls.
Description
Technical field
The present invention relates to a kind ofly be used to make the silane coupling agent of inorganic thin film layer and plastic basis material driving fit, the plastics that have inorganic thin film, mould internal shaping to be shaped to use decorating film with decorating film and inserts.
Background technology
All the time, by the surface coated silane coupling agent of plastic basis material and and then form the difference of the composite base material that the inorganic thin film that is made of aluminium, tin etc. obtains (below be called band inorganic thin film plastics) according to the kind of the material that constitutes inorganic thin film and thickness etc., can be preferably used as wrapping material, transparent conductive sheets, film capacitors etc. such as bottle, lid and choke film.In addition, in the membranaceous band inorganic thin film plastics, have the plastics of the aluminium lamination as thin as a wafer about tens of nm, be widely used as decorating film (being also referred to as transfer foil) especially and use member.
But, for band inorganic thin film plastics,, all have the problem that produces the albefaction position under the high temperature at the inorganic thin film face regardless of its form.In addition, when band inorganic thin film plastics when being membranaceous, under hot conditions is shaped the situation of processing, not only can on the inorganic thin film face of the Fei Jia Ministry of worker, produce the albefaction position, also can on the inorganic thin film face of working position, produce the crackle that interference fringe and range estimation just can be judged, infringement technical feature (gas barrier property, electromagnetic wave shielding performance etc.) and designability that inorganic thin film possessed.
About crack problem, known for example in patent documentation 1, can solve by the three liquid type silane coupling agents that contain acrylic resin, melamine resin and polyisocyanate compounds, but do not mention albinism.In addition,, also use urethane resin or vibrin sometimes, but under the situation of using the silane coupling agent of making like this, the bad order of inorganic thin film face in addition, also is difficult to eliminate problems such as above-mentioned albefaction, crackle as the base resin of silane coupling agent.
[background technology document]
[patent documentation]
[patent documentation 1] TOHKEMY 2004-122456 communique
Summary of the invention
Problem of the present invention is, a kind of novel silane coupling agent that is used to make the plastics of being with inorganic thin film is provided, it connects airtight with inorganic thin film and plastic basis material, even and will at high temperature process also with the inorganic thin film plastics and can not produce on the inorganic thin film face by the visual crackle that can judge, interference fringe and tangible albefaction position.
The inventor is through further investigation repeatedly, found that, utilization comprises second-order transition temperature that (A) have carboxylate anion's group for-5～120 ℃ acrylic copolymer and the band inorganic thin film plastics silane coupling agent that (B) has the polyaziridine compound of 3 aziridinyls at least, can solve above-mentioned problem.
Utilize silane coupling agent of the present invention, can form level and smooth inorganic thin film on the plastic basis material surface.In addition, when inorganics is metal, the gloss excellence of inorganic thin film.In addition, inorganic thin film and plastics are connected airtight well.
In addition, even the band inorganic thin film plastics that obtained by silane coupling agent of the present invention also are being difficult to produce albefaction position (below, this effect is called " anti-albefaction ") at the inorganic thin film face under the hot conditions.Particularly film material even form processing under hot environment, also is difficult to produce crackle, interference fringe and albefaction position (following this effect is called " the anti-processibility " that can judge by range estimation on inorganic thin film.)。
Therefore, band inorganic thin film plastics of the present invention except useful in exercise uses such as wrapping material, transparent conductive sheets, film capacitor such as bottle, bottle cap and choke film, also be preferably used as inserts be shaped with the member of decorating film and the mould internal shaping of the processing of at high temperature implementing to be shaped with the member of decorating film.
Description of drawings
Fig. 1 is the outward appearance (electron micrograph, 3000 times) that processibility is evaluated as 6 aluminium-vapour deposition film.
Fig. 2 is the outward appearance (electron micrograph, 3000 times) that processibility is evaluated as 5 aluminium-vapour deposition film.
Fig. 3 is the outward appearance (electron micrograph, 3000 times) that processibility is evaluated as 4 aluminium-vapour deposition film.
Fig. 4 is the outward appearance (electron micrograph, 3000 times) that processibility is evaluated as 3 aluminium-vapour deposition film.
Fig. 5 is the outward appearance (electron micrograph, 3000 times) that processibility is evaluated as 2 aluminium-vapour deposition film.
Fig. 6 is the outward appearance (electron micrograph, 3000 times) that processibility is evaluated as 1 aluminium-vapour deposition film.
Embodiment
Silane coupling agent of the present invention comprises second-order transition temperature that (A) have carboxylate anion's group and has the polyaziridine compound (below be called (B) composition) of 3 aziridinyls and the aziridinyl ring opening catalyst (C) that adds as required (below be called (C) composition) at least for-5～120 ℃ acrylic copolymer (below be called (A) composition), (B).
As (A) composition, so long as have described second-order transition temperature and intramolecularly has carboxylate anion's group (COO
-) acrylic copolymer, just can use various known materials and not have particular restriction.
As the preferred form of (A) composition, can enumerate the material that the multipolymer neutralization that will (a1) α, beta-unsaturated carboxylic acid (below be called (a1) composition), (a2) (methyl) alkyl acrylate and/or styrenic (below be called (a2) composition) and other unsaturated monomer reaction of (a3) adding as required be formed forms.
As (a1) composition, for example can enumerate α, β-unsaturated monocarboxylic acids such as vinylformic acid, methacrylic acid, Ba Dousuan, iso-crotonic acid; The monoesters of fumaric acid, toxilic acid α such as (acid anhydrides), β-unsaturated dicarboxylic acid and this α, β-unsaturated dicarboxylic acid and various alcohol etc.
As (a2) composition, promptly (methyl) alkyl acrylate for example can be enumerated (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) lauryl acrylate, (methyl) vinylformic acid stearyl, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid ring pentyl ester, (methyl) isobornyl acrylate etc.Need to prove that (a2) alkyl of composition does not have the functional group that hydroxyl etc. contains reactive hydrogen.In addition, the carbonatoms of this alkyl is generally about 1～20, is preferably about 1～8 more preferably 1～5.In addition, as styrenic, for example can enumerate vinylbenzene, alpha-methyl styrene, t-butyl styrene, dimethyl styrene etc.
As (a3) composition, for example can enumerate hydroxyl (methyl) esters of acrylic acids such as (methyl) vinylformic acid hydroxyl methyl esters, (methyl) Hydroxyethyl acrylate, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) vinylformic acid hydroxyl cyclohexyl, (methyl) vinylformic acid 4-(methylol) cyclohexyl methyl esters, 2 hydroxy propanoic acid 4-(methylol) cyclohexyl methyl esters, (methyl) crylic acid hydroxylphenyl ester, N-(2-hydroxyethyl) acrylamide, N-(1-methyl-2-hydroxyethyl) acrylamide; (methyl) acrylic amide; Unsaturated sulfonic acid Class; Aminoalkyl group is the unsaturated monomer class; Poly (oxyalkylene) base system unsaturated monomer class; Chlorosilane system (methyl) esters of acrylic acid; (gathering) siloxanes list (methyl) esters of acrylic acid; Fluoroalkyl (list) esters of acrylic acid etc.
(a1) composition and (a2) the use mole % of composition do not have particular determination, be followed successively by usually about 7～70 moles of %, about 30～93 moles of %, be preferably about 13～45 moles of %, 55～87 moles of %.In addition, when using (a3) composition, (a1) the use mole % of composition of composition～(a3) be followed successively by usually about 7～70 moles of %, about 29～92 moles of %, about 1～60 mole of %, be preferably 13～45 moles of %, 52～84 moles of %, 3～20 moles of %.
(A) manufacture method of composition does not have particular determination, for example can enumerate in the presence of polymerization starter and organic solvent, usually about 80～180 ℃, the composition of described (a1) composition～(a3) is carried out after the radical polymerization about 1～20 hour, with the polymkeric substance neutral method of neutralizing agent with gained.
As polymerization starter, can enumerate benzoyl peroxide, the peroxidation 2 ethyl hexanoic acid tert-butyl ester, 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile) etc.
As organic solvent, can enumerate ethers (not comprising and the suitable material of ether-ether class described later) such as alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, ethylene glycol (not comprising the material suitable with the ether-ether class), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether with ether described later; Ether-ether such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether class; Ketone such as acetone, methyl ethyl ketone; Dimethyl formamide etc.
As neutralizing agent, can enumerate ammonia; Primary amine classes such as single methylamine, mono aminoethane, dibutyl amine, hexahydroaniline; Secondary amine such as dimethylamine, diethylamine class; Tertiary amines such as Trimethylamine 99, triethylamine; Alkali metal hydroxide such as sodium hydroxide, potassium hydroxide; Alkaline-earth metal oxyhydroxide such as magnesium hydroxide etc.Wherein, when using tertiary amines and/or ammonia, the anti-albefaction of tunicle and processibility, anti-dissolubility etc. are good especially, so preferred.The usage quantity of neutralizing agent is generally 80～300 moles of scopes about % with respect to the carboxyl that acrylic copolymer has.
Mainly consider that from the viewpoint of anti-albefaction and particularly processibility (A) second-order transition temperature of composition is-5～120 ℃, is preferably 40～110 ℃.In addition, this second-order transition temperature is a measured value.
(A) content of carboxylate anion's group of composition is not particularly limited, and is generally about 0.5～8mmol/g, is preferably 1～5mmol/g, and in the time of in this scope, it is good that particularly anti-albefaction and anti-processibility are tended to become.In addition, so-called " content of carboxylate anion's group " is meant the mole number of carboxylate anion's group contained in 1g (A) composition (being converted into nonvolatile component) to be calculated value.
(A) weight-average molecular weight of composition (the polystyrene conversion value that obtains by gel permeation chromatography) also is not particularly limited, and mainly considers from the viewpoint of anti-albefaction and processibility, is generally about 3000～100000, is preferably 10000～80000.
As (B) composition, so long as contain the material of 3 aziridinyls at least, just can not have and especially restrictedly use various known materials (with reference to No. 4382135, United States Patent (USP), TOHKEMY 2003-104970 number etc.) at intramolecularly.Particularly, the compound of preferably representing with following general formula.
(in the formula, X
1Expression hydrogen, the alkyl of carbonatoms 1～6 or the hydroxyalkyl of carbonatoms 1～3, R
1Expression hydrogen or methyl, R
2And R
3The alkyl of representing hydrogen or carbonatoms 1～6 respectively.)
As the compound of representing with this formula, can enumerate tetramethylol methane-three-(β-aziridinyl propionic ester), trimethylolpropane tris (β-aziridinyl propionic ester), reach glyceryl three (β-aziridinyl propionic ester) etc.
As other (B) composition, can enumerate four aziridine cpds such as four aziridinyl m-xylene diamines, four aziridinyl methyl p dimethylamines, tetramethyl-propane four aziridinyl propionic esters etc.
In addition, can and use neopentyl glycol two (β-aziridinyl propionic ester), 4 with (B) composition, 4 '-isopropylidene biphenol two (β-aziridinyl propionic ester), 4,4 '-methylene radical biphenol two phenodiazine third acridine compounds such as (β-aziridinyl propionic ester) and 2-methylaziridine, 2-ethyl aziridine, 2,2-dimethyl aziridine, 2, single aziridine cpds such as 3-dimethyl aziridine, 2-phenyl aziridine.
(B) content of the aziridinyl of composition is not particularly limited, and when especially considering anti-albefaction and anti-processibility etc., is generally about 3～11mmol/g, preferably in the scope of 5～9mmol/g.In addition, so-called " content of aziridinyl " is meant the mole number of aziridinyl contained in 1g (B) composition to be calculated value.
Particularly consider, can use (C) composition as required from the purpose that anti-albefaction and anti-processibility are improved.As concrete example, can enumerate acid catalysts such as tosic acid, hydrochloric acid, bromic acid, acid iodide, fluoric acid, fluosulfonic acid, sulfuric acid, phosphoric acid and diaryl group iodized salt, triarylsulfonium salt, Er Fang Ji phosphonium salt etc.Wherein, for easy processing, preferred acid catalyzer, preferred especially tosic acid.In addition, as required, can and use above-mentioned neutralizing agent, preferably use ammonia with (C) composition.This neutralizing agent can be used as the aqueous solution and uses.
Silane coupling agent of the present invention be utilize various known method with (A) composition, (B) composition and (C) composition of adding as required mixes and.(A) composition and (B) the content ratio of composition be not particularly limited, particularly consider from the viewpoint of anti-albefaction and anti-processibility, usually, [(A) usage quantity (g) (being converted into nonvolatile component) of content (mmol/g) * (A) composition of carboxylate anion's group of composition)/[(B) usage quantity (g) (being converted into nonvolatile component) of the content of the aziridinyl of composition (mmol/g) * (B) composition] be generally about 0.01～10, preferably in 0.1～2 scope.In addition, (C) usage quantity of composition does not have particular determination, usually, convert with solids component with respect to (B) composition count about 1～15 weight %, the scope of preferred 5～10 weight %.
Silane coupling agent of the present invention can be to use described organic solvent, water (ion exchanged water etc.) as the form of the solution of solvent.As this organic solvent, preferred above-mentioned alcohols.In addition, with an organic solvent reach water both the time, usually weight ratio is followed successively by about 9/1～1/9.
The nonvolatile component of silane coupling agent of the present invention is not particularly limited, and is generally about 5～50 weight %.In addition, usually, in this nonvolatile component, (A) composition, (B) composition and (C) the shared amount of composition be followed successively by about 42～85 weight %, about 15～58 weight % and about 0～8 weight %.
In silane coupling agent of the present invention, can also cooperate other additive such as flow agent, antioxidant, UV light absorber, silica gel, filler.
Band inorganic thin film plastics of the present invention have plastic basis material, by silane coupling agent of the present invention form the layer and by inorganic thin film forms layer.As plastic basis material, can enumerate polyester, polyvinyl chloride, polymeric amide, polyimide, polycarbonate, polyethylene, polypropylene etc., these compounds also can carry out surface treatments such as corona discharge.
This plastic basis material is a structure (except the material suitable with plastic film) or membranaceous such as spherical, cylindrical, rectangular-shaped, tabular, also can have concavo-convex and curved surface in the part on surface.The thickness of membranaceous plastic basis material is not particularly limited, and is generally about 12～200 μ m.
As the chemical substance that forms inorganic thin film, can enumerate metal oxides such as metal such as aluminium, gold and silver, palladium, tin or aluminum oxide, stannic oxide, tin indium oxide, titanium oxide, silicon oxide, they can and be used.
The method of making band inorganic thin film plastics of the present invention is not particularly limited, for example can enumerate silane coupling agent of the present invention is used after various known method are coated on the above-mentioned plastic basis material, make undercoat solidify (treatment condition: common about 60～165 ℃, about 10 seconds～5 minutes), then on the undercoat surface, form the method for above-mentioned inorganic thin film kind.
As the coating process of silane coupling agent, can enumerate that spraying, roller coat, contrary print roll coating, intaglio plate coating, scraper coating, rod are coated with, spot printing etc.Glue spread does not have particular determination, counts 0.01～10g/m with nonvolatile component usually
2About.
As the method that forms inorganic thin film, can enumerate various known physical methods (vacuum thermal evaporation, sputter etc.), chemical process (chemical gas phase reaction etc.).In addition, the thickness of inorganic thin film is generally about 5～800nm.
Band inorganic thin film plastics of the present invention can also possess various functional layers such as release layer, hard coat, hard coat immovable bed, decorative pattern China ink liquid layer, bond layer.
In the band inorganic thin film plastics of the present invention, plastic basis material is that membranaceous material (band inorganic thin film plastic film) is particularly useful for being shaped with the parts of decorating film with decorating film or inserts as the mould internal shaping.At this moment, preferably this plastic basis material is that polyester film, inorganic thin film layer are aluminium lamination and/or the tin layer about 5～50nm.
Embodiment
Below, by embodiment and comparative example the present invention is described in more details, but the present invention is not limited in this scope.In addition, the expression of " part " among embodiment weight standard.
In each example, the value of second-order transition temperature for using commercially available determining instrument (goods name " DSC8230B ", motor of science (strain) system) to record.In addition, number-average molecular weight is to use commercially available gel permeation chromatograph device (making name " HLC-8220GPC ", eastern Cao (strain) system) to measure the value that obtains.
＜(A) preparation of composition 〉
Production Example 1
In the reaction vessel that has whipping appts, thermometer, reflux exchanger, dropping funnel and nitrogen ingress pipe, add 2055.6 parts of 150.0 parts of 500.0 parts of the commercially available styrene acrylic copolymers that contains carboxyl (synthetic (strain) manufacturing of goods name " ARUFON-UC3920 ", East Asia, nonvolatile component 100%, (a1) composition are that vinylformic acid, (a2) composition are vinylbenzene), Virahol (below be called IPA), ion exchanged water (below be called IW), 28% ammoniacal liquor (below be called 28%NH
3) 155.8 parts, 45 ℃ of insulations 3 hours, obtain second-order transition temperature (below be called Tg) and be 104 ℃, carboxylate anion's group content (below be called CA) is that the solution (nonvolatile component (below be called NV) of (A-1) composition of 15500 is 20% for 4.3mmol/g, weight-average molecular weight (below be called Mw)).
Production Example 2
In the reaction vessel identical with Production Example 1, add 72 parts of 151.2 parts of 16.8 parts of methacrylic acids (below be called MAA), methyl methacrylate (below be called MMA), methacrylic acid 2-hydroxyl ethyl ester (below be called 2-HEA), 2,1.2 parts of 2 '-azos two (methylbutyronitrile) (below be called ABN-E), 360 parts of IPA keep 5 hours (above is the pre-polymerization operation) at 80 ℃ under nitrogen gas stream.Then add 2.4 parts of ABN-E, reaction system further is incubated 3 hours (above is the post polymerization operation) near uniform temp.Then, add 23.6 parts of 288.2 parts of 288.2 parts of IPA, IW, triethylamines (below be called TEA) neutralize (above be neutralization, dilution operation).The rerum natura of (A-2) composition that obtains thus is as shown in table 1.
Production Example 3～6, comparison Production Example 1～3
Except that the raw material that uses umber as shown in table 1,, obtain composition of (A-3) composition～(A-6) and various solution of composition of (AC-1) composition of usefulness～(AC-3) relatively by the method identical with Production Example 2.Each rerum natura is shown in table 1.
[table 1]
AA: vinylformic acid
BA: n-butyl acrylate
28%NH
3: 28% ammoniacal liquor
Compare Production Example 4
In the reaction vessel identical with Production Example 1, add 256 parts of 479 parts of terephthalic acids, 402 parts of m-phthalic acids, 87 parts of nonane diacids, ethylene glycol, 1,23 parts of 354 parts of 6-hexylene glycols and glycerol, the stirring heating reaction system makes its dissolving.Then, the water that reaction system generates in dehydration condensation is removed, simultaneously, utilized 3 hours from 160 ℃ and be warming up to 200 ℃, further 200 ℃ of insulations 1 hour.Then add 0.16 part of antimonous oxide.Then, reaction vessel is linked to each other the polycondensation 1 hour of under 235 ℃, 2.8kPa, reducing pressure with the vacuum decompression device.Then, remove decompression state, reaction system is cooled to 150 ℃, in reaction system, add 119 parts of trimellitic acid 1,2-anhydrides, be incubated 1 hour.Next, add 1997 parts of methyl iso-butyl ketone (MIBK), methyl ethyl ketone makes it uniform dissolution for 1997 parts, obtain Tg and be 19 ℃, CA and be 0.4mmol/g, Mw and be the solution (NV is 35 weight %) of 30000 vibrin (PE-1).
Compare Production Example 5
In the reaction vessel identical, add commercially available polycarbonate diol (goods name " ニ Star Port ラ Application 980R ", number-average molecular weight 2000 with Production Example 1; Japanese polyurethane industry (strain) system) 151.4 parts of 362.3 parts, isophorone diisocyanate, 2,36.3 parts of 2-dimethylol propionic acids, 550 parts of methyl ethyl ketones, under 80 ℃ of conditions, carry out the ammonia esterification 10 hours, obtain 1100 parts of the urethane prepolymers of isocyanate group end.Next, this prepolymer is added drop-wise in the chain extension agent solution (24.6 parts of triethylamines, 41.1 parts of Virahols, 3.6 parts of isophorone diamines, 12.1 parts of adipic dihydrazides, 434.9 parts of methyl ethyl ketones) that is in whipped state, mixes the total overall reaction system.Afterwards, 60 ℃ of lasting stirring reaction systems 2 hours, make to increase chain reaction and finish, obtaining Tg is that 0.5mmol/g, Mw are the aqueous solution (NV is 35 weight %) of 14000 urethane resin (PU-1) for-10 ℃, CA.
The preparation of＜silane coupling agent 〉
Embodiment 1
With 5 parts of (A-1) compositions, tetramethylol methane-three-(β-aziridinyl propionic ester) (goods name " TAZO ", mutually pharmaceutical worker's (strain) make, the content 7mmol/g of aziridinyl) 0.12 part of (below be called TAZO) 1.2 parts, tosic acid (below be called PTS), 28%NH
30.04 part, 8.4 parts of mixings in beaker of 8.4 parts of IPA, IW, preparation NV is the silane coupling agent of 10 weight %.
Embodiment 2～15, comparative example 1～43
Except that the raw material that uses umber shown in each table, by the method identical, preparation silane coupling agent with embodiment 1.
[table 2]
[table 3]
PZ-33: trimethylolpropane tris (β-aziridinyl propionic ester) (the content 7mmol/g of goods name " ケ ミ タ イ ト PZ-33 ", (strain) Japanese catalyst manufacturing, aziridinyl)
SV-02: carbodiimide is solidifying agent (trade(brand)name " Carbodilite SV-02 ", day are spun the content 2.3mmol/g of chemical (strain) manufacturing, carbodiimide clearly)
WS-700: oxazoline is solidifying agent (the content 4.5mmol/g of trade(brand)name " EPOCROS WS-700 ", (strain) Japanese catalyst Zhi, oxazolinyl)
EX-612: epoxy is solidifying agent (the content 5.9mmol/g of trade(brand)name " DENACOL ", Nagase chemteX (strain) manufacturing, epoxy group(ing))
(A)/(B): [(A) usage quantity (g) (being converted into nonvolatile component) of content (mmol/g) * (A) composition of carboxylate anion's group of composition]/[(B) usage quantity (g) (being converted into nonvolatile component) of the content of the aziridinyl of composition (mmol/g) * (B) composition]
The preparation of＜aluminium-vapour deposition plastic film and evaluation 〉
Use rod to be coated with the silane coupling agent of machine gained in commercially available PET film (goods name " E5100 ", Japan's weaving (strain) are made, 38 μ m thick) coating embodiment 1, making it dry film thickness is 1 μ m, then with coated film dry (150 ℃, 60 seconds) in the recirculating air drying machine.
Next, the desciccator diaphragm of gained is installed on the commercially available evaporation coating device (goods name " NS-1875-Z ", Western Hills are made institutes' (strain) and made), the thickness that obtains the evaporation layer is the aluminium-vapour deposition film of 50nm.With the experimental film of this film as embodiment 1.For other embodiment and comparative example, same operation, preparation experimental film.
(outward appearance)
Outward appearance according to the evaporation face of the experimental film of following standard visual assessment embodiment 1.Experimental film to other embodiment and comparative example also carries out same evaluation.The result is shown in table 4 and table 5.
3 ... the evaporation face does not produce albefaction
2 ... produce few albefaction on the whole evaporation face
1 ... produce serious albefaction and interference fringe on the whole evaporation face
(connecting airtight property)
On the evaporation face of the experimental film of embodiment 1, paste self adhesive tape (goods name " Cellotape ", Mi Qibang (strain) make), vertically peel off well.In addition, the experimental film to other embodiment and comparative example also carries out same evaluation.Because the aluminium-vapour deposition film can not produce and peel off in any case, be 3 entirely in table 4 and table 5 therefore.
(anti-albefaction)
In 150 ℃ recirculating air drying machine, heat the outward appearance of the evaporation face after 60 minutes according to the experimental film of following standard visual assessment embodiment 1.The result is shown in table 4 and table 5.
4 ... the evaporation face does not produce albefaction and interference fringe
3 ... the local generation of evaporation face albefaction does not produce interference fringe
2 ... produce few albefaction and interference fringe on the whole evaporation face
1 ... produce serious albefaction and interference fringe on the whole evaporation face
(processibility)
(to make it dry film thickness be 1 μ m to the silane coupling agent of gained among the coating embodiment 1 of goods name " comoglas ", the manufacturing of (strain) Kuraray, 5cm * 5cm * 1mm) to commercially available vinylformic acid panel, by in the recirculating air drying machine under 150 ℃ of conditions dry 60 seconds, preparation was used for the test panel of anti-workability test.In addition, the silane coupling agent of other embodiment and comparative example is made test panel similarly respectively.
In addition, as the crooked utensil of described test panel, prepare that (15cm * 5cm * 1mm) is from the utensil of 60 ° of gained of middle bending with aluminium sheet.
Next, with the heating back taking-up in (250 ℃) in the recirculating air drying machine of above-mentioned crooked utensil, on the curved edges of this utensil of the condition of high temperature, above-mentioned test panel was pushed about 3 seconds from vinylformic acid panel side, crooked afterwards about 80 °, then according to the state of the aluminium-vapour deposition layer of following standard visual assessment crooked position.In addition, the test panel of other embodiment and comparative example is also carried out same evaluation.The result is shown in table 4 and table 5.
6 ... the metal evaporation position does not have breakage and peels off, and does not have fuzzy and interference fringe, and range estimation judges that outward appearance is better than 5.
5 ... the metal evaporation position does not have breakage and peels off, and does not have fuzzy and interference fringe
4 ... the metal evaporation position does not have breakage and peels off, and a small amount of bluring only arranged, but does not have interference fringe
3 ... the metal evaporation position does not have breakage and peels off, and a small amount of fuzzy and interference fringe is only arranged
2 ... there is tiny breakage at the metal evaporation position and peels off, and serious fuzzy and interference fringe is arranged
1 ... there is bigger breakage at the metal evaporation position and peels off, and serious fuzzy and interference fringe is arranged
Need to prove,, primary coat face (layer) is excessively stretched along the bending direction of panel owing to use thick vinylformic acid panel.Its result is easy to generate crackle on the aluminium-vapour deposition layer.Ke Ke test conditions is the condition at the physical device of mold-in injection shaping like this.
[table 4]
[table 5]
Embodiment 16～20, comparative example 44～46
The preparation and the evaluation of＜tin evaporation plastic film 〉
It is 1 μ m that the silane coupling agent that uses coating machine to be coated with gained among the embodiment 1 on described PET film makes it dry film thickness, then with coated film dry (150 ℃, 60 seconds) in the wind circulation dryer.Next, utilize described evaporation coating device, obtaining the evaporation layer thickness is the tin vapor-deposited film of 50nm.For the silane coupling agent of embodiment 8,11,13,15 and comparative example 29,31,33, operation obtains the tin vapor-deposited film too.Next, according to the method and the benchmark of above-mentioned test subject the smoothness of each film, connecting airtight property, anti-albefaction and processibility are estimated.The results are shown in table 6.
[table 6]
Claims (12)
1. band inorganic thin film plastics silane coupling agent, its second-order transition temperature that comprises that (A) have carboxylate anion's group is-5～120 ℃ acrylic copolymer and the polyaziridine compound that (B) has 3 aziridinyls at least.
2. silane coupling agent as claimed in claim 1, wherein, (A) composition is that the multipolymer neutralization that (a1) α, beta-unsaturated carboxylic acid, (a2) (methyl) alkyl acrylate and/or styrenic and other unsaturated monomer reaction of (a3) adding as required form is formed.
3. silane coupling agent as claimed in claim 1 or 2, wherein, (A) carboxylate anion's group of composition is 0.5～8mmol/g.
4. as each described silane coupling agent in the claim 1～3, wherein, (A) weight-average molecular weight of composition is 3000～100000.
5. as each described silane coupling agent in the claim 1～4, wherein, (B) composition is represented with following general formula,
In the formula, X
1Expression hydrogen, the alkyl of carbonatoms 1～6 or the hydroxyalkyl of carbonatoms 1～3, R
1Expression hydrogen or methyl, R
2And R
3The alkyl of representing hydrogen or carbonatoms 1～6 respectively.
6. as each described silane coupling agent in the claim 1～5, wherein, further comprise (C) aziridinyl ring opening catalyst.
7. silane coupling agent as claimed in claim 6, wherein, (C) composition is a tosic acid.
8. as each described silane coupling agent in the claim 1～7, wherein, (A) composition and (B) the content ratio of composition, promptly
[content of carboxylate anion's group of described (A) composition * be converted into the usage quantity of (A) composition of nonvolatile component]/[(B) content of the aziridinyl of composition * be converted into the usage quantity of (B) composition of nonvolatile component]
In 0.01～10 scope, the unit of the content of described carboxylate anion's group and the content of aziridinyl is mmol/g, (A) usage quantity of composition and (B) unit of the usage quantity of composition be g.
9. band inorganic thin film plastics, the layer that it contains plastic basis material, is formed by each described silane coupling agent in the claim 1～8 and by inorganic thin film constitute layer.
10. band inorganic thin film plastics as claimed in claim 9, wherein, plastic basis material is membranaceous.
11. one kind with the mould internal shaping decorating film of the described band inorganic thin film of claim 10 plastics as member.
12. one kind with the inserts shaping decorating film of the described band inorganic thin film of claim 10 plastics as member.
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| JP2010041532 | 2010-02-26 | ||
| JP2010-041532 | 2010-02-26 |
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| JP (1) | JP5655629B2 (en) |
| KR (1) | KR20110098665A (en) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103540217A (en) * | 2013-10-08 | 2014-01-29 | 广东雅图化工有限公司 | Aziridine crosslinked acrylate resin two-component water-based automobile coating and preparation method thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6154872B2 (en) * | 2014-12-27 | 2017-06-28 | 三菱ケミカル株式会社 | Laminated polyester film |
| JP6113209B2 (en) * | 2015-01-29 | 2017-04-12 | 三菱樹脂株式会社 | Adhesive film |
| JP6015877B1 (en) * | 2015-09-25 | 2016-10-26 | 東洋インキＳｃホールディングス株式会社 | Decorative film, method for producing the same, and decorative molded body |
| WO2018151089A1 (en) | 2017-02-14 | 2018-08-23 | 出光ユニテック株式会社 | Laminate, molded article, and method for producing molded article |
| JP2021116374A (en) | 2020-01-28 | 2021-08-10 | 荒川化学工業株式会社 | Undercoat agent, cured product, and laminate |
| JP2022139500A (en) | 2021-03-12 | 2022-09-26 | 荒川化学工業株式会社 | Undercoat agent, coating agent kit, cured product and laminate |
| JP7441356B1 (en) | 2023-04-13 | 2024-02-29 | Ｄｉｃグラフィックス株式会社 | Water-based ink and laminates |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101538435A (en) * | 2008-03-21 | 2009-09-23 | 荒川化学工业株式会社 | Antistatic coating agent |
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| JPS58129068A (en) * | 1982-01-27 | 1983-08-01 | Isamu Toryo Kk | Two-part type aqueous coating material composition for repairing automobile |
| JPS61174542A (en) * | 1985-01-16 | 1986-08-06 | イー・アイ・デユポン・ド・ネモアース・アンド・コンパニー | Improved two-layer formation for application of antistatic composition for polyester support |
| JPH0699578B2 (en) * | 1988-08-15 | 1994-12-07 | 帝人株式会社 | Easy-adhesive polyester film |
| KR20070114401A (en) * | 2005-03-24 | 2007-12-03 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Metallized films and articles containing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101538435A (en) * | 2008-03-21 | 2009-09-23 | 荒川化学工业株式会社 | Antistatic coating agent |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103540217A (en) * | 2013-10-08 | 2014-01-29 | 广东雅图化工有限公司 | Aziridine crosslinked acrylate resin two-component water-based automobile coating and preparation method thereof |
| CN103540217B (en) * | 2013-10-08 | 2016-06-01 | 雅图高新材料有限公司 | The double-component aqueous car paint of acrylate resin that a kind of aziridine is crosslinked and its preparation method |
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| CN102167942B (en) | 2016-02-24 |
| KR20110098665A (en) | 2011-09-01 |
| TWI516375B (en) | 2016-01-11 |
| JP5655629B2 (en) | 2015-01-21 |
| TW201141707A (en) | 2011-12-01 |
| JP2011195835A (en) | 2011-10-06 |
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