CN101981068B - Resin composition, hard-coating agent, film, and method for production of molded article - Google Patents
Resin composition, hard-coating agent, film, and method for production of molded article Download PDFInfo
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- CN101981068B CN101981068B CN200980110485.7A CN200980110485A CN101981068B CN 101981068 B CN101981068 B CN 101981068B CN 200980110485 A CN200980110485 A CN 200980110485A CN 101981068 B CN101981068 B CN 101981068B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
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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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- 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
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
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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
- C08J2429/00—Characterised by the use of 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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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
- C08J2433/00—Characterised by the use 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; Derivatives of such polymers
- C08J2433/04—Characterised by the use 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; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/08—Homopolymers or copolymers of acrylic acid esters
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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
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
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- General Chemical & Material Sciences (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
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- Treatments Of Macromolecular Shaped Articles (AREA)
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Abstract
Disclosed is a resin composition which is characterized by comprising a polyfunctional polymerizable compound having two or more acryloyl groups and a compound capable of being added to an acryloyl group.
Description
Technical field
The present invention relates to the manufacture method of resin combination, hard-coating agent, film and formed body.
Background technology
All the time, in the thin film switch (membrane switch) of household appliances or the displaying tank (ダ ミ mono-narrow-necked earthen jar) of vending machine etc., all in use, be coated with the film of thermohardening type resin.
In addition, coating has been solidified with thermohardening type resin-phase day by day more universal with film than the moulding of ultraviolet curing resin with better scuff resistance.Particularly, because the electronics casings such as mobile phone, portable music player, contact panel and automotive interior trim material have requirement to hardness, scuff resistance, stain resistance, reflecting feel etc., therefore in these purposes, bring into use coating to solidify the film for moulding (referring to patent documentation 1-3) of ultraviolet curing resin.
Prior art document
Patent documentation 1: No. 00/34396 text of International Publication
Patent documentation 2: JP 2005-8717 communique
Patent documentation 3: JP 2004-305863 communique
Summary of the invention
The problem that invention will solve
Hardness and the scuff resistance of film that has been coated with thermohardening type resin is low, easily produces scar, thereby significantly deteriorated in appearance.On the other hand, the moulding that ultraviolet curing resin has been solidified in coating is with film because rigidity produces by force and easily crack, so formability is low, can only be for the moulding of more smooth structure.
The present invention makes in view of above problem, and take provides hardness and scuff resistance is high and the manufacture method of the resin combination of good forming ability, hard-coating agent, film and formed body is object.
The means of dealing with problems
Below, the present invention is described in detail.
(1) resin combination of the present invention
Resin combination of the present invention is characterised in that, it contains and has the multifunctional polymerizable compound of two above acryls and can carry out with acryl the compound of addition reaction.
Resin combination of the present invention is carrying out under the state of one-step solidification, is also difficult for producing the flexibility in crack while not only having moulding, is also difficult for producing tackiness.In addition, resin combination of the present invention under the state that has carried out regelate hardness and scuff resistance all good.
In addition, the implication of so-called one-step solidification is to carry out addition reaction with acryl.In addition, so-called regelate is to carry out radical polymerization by irradiation ultraviolet radiation, electron rays isoreactivity energy-ray.The multifunctional polymerizable compound with two above acryls the present invention relates to is because free radical reaction is very high, and has rapidly-curable and high rigidity, therefore has advantage.As the multifunctional polymerizable compound with two above acryls, for example can enumerate 1, 4-butylene glycol diacrylate, 1, 6-hexanediyl ester, neopentylglycol diacrylate, polyethyleneglycol diacrylate, hydroxyl trimethylacetic acid neopentylglycol diacrylate, diacrylate two cyclopentenes esters, caprolactone modification diacrylate two cyclopentenes esters, oxyethane modified phosphate diacrylate, allylation diacrylate cyclohexyl, isocyanuric acid ester diacrylate, Viscoat 295, Dipentaerythritol triacrylate, propionic acid modification Dipentaerythritol triacrylate, pentaerythritol triacrylate, epoxy pronane modification Viscoat 295, three (acryloxy ethyl) isocyanuric acid ester, Dipentaerythritol five acrylate, propionic acid modification Dipentaerythritol five acrylate, dipentaerythritol acrylate, caprolactone modification dipentaerythritol acrylate etc.
The acrylate surface hardness that functional group's number is more is higher, is therefore preferred.It can be used alone and also can two or more mixing use.The multifunctional polymerizable compound with two above acryls can be also prepolymer for monomer, in addition, can be also urethane acrylate, ethoxy propylene acid esters, polyester acrylate etc.
The compounds of the compound that can carry out addition reaction with acryl using in the present invention for carrying out addition reaction with the multifunctional polymerizable compound with two above acryls.By this addition reaction, resin combination is carried out to one-step solidification (B stage), so the tackiness of resin combination disappears or reduces.Utilize this feature, by apply the condition that promotes addition reaction after resin combination is coated on film, the bonding in the time of can preventing bonding between film and moulding between film and mold.Can carry out the compound of addition reaction with acryl so long as there is the compound of nucleophilicity, but concrete preferred amines compound.
Amine compound is the material that contains primary amine or secondary amine, can enumerate such as methylamine, quadrol, diethylenetriamine, Triethylenetetramine (TETA), tetren, penten, hexamethylene-diamine, aniline, phenylethylamine, Symmetrel, piperazine, contain the amino low molecular weight amines such as silane coupling agent.The implication of the low molecular weight amine described in the present invention is such as being the ethylene sulfonamide derivativess such as DETA (diethylenetriamine), TETA (Triethylenetetramine (TETA)), PEHA (five ethylidene thiamines), and its molecular weight is suitable in the scope of for example 50-400.In addition,, as amine compound, also can use the polyamine of the amino structure with repetition.By being combined with low molecular weight amine and polyamine, can easily adjust the solidified nature of resin combination.In addition, if be combined with low molecular weight amine and polyamine, at resin combination during the state in one-step solidification, the rubber viscosity of more having difficult labour.The molecular weight of polyamine is suitable in 10,000-200,000 scope for example.
The consumption of amine compound depends on the amine value state of amine compound used; the multifunctional polymerizable compound with two above acryls with respect to 100 weight parts; preferably in the scope of 0.1-50 weight part; more preferably in the scope of 0.5-30 weight part, in the scope particularly preferably in 5-25 weight part.In the inadequate situation of one-step solidification of resin combination, can be by increasing the amount of allocating into of amine compound, or improve polyamine shared ratio in amine compound, can improve curing performance.On the other hand, in the situation that the storage period of resin combination, (pot life) was short, can be by reducing the amount of allocating into of amine compound, or reduce polyamine shared ratio in amine compound, thus extend storage period.In addition, the amine value state of compound is higher, and the reactivity of amine compound is higher, can reduce the addition of amine compound and surface physical properties is still good, is therefore preferred.
By the described compound that can carry out addition reaction with acryl is coordinated with temperature sensibility catalyzer, can easily take into account the storage period of one-step solidification and resin combination.That is, because temperature sensibility catalyzer does not have catalytic activity (or catalytic activity is low) at normal temperatures, therefore can extend the storage period of resin combination, and owing to can bringing into play rapidly activity at high temperature, therefore can improve one-step solidification.In addition, when coordinating with temperature sensibility catalyzer, during state at resin combination in one-step solidification, the rubber viscosity of more having difficult labour.
As the specific examples of temperature sensibility catalyzer, particularly preferably as the DBU (1,8-diazabicyclo [5.4.0], 11-7-alkene) of highly basic and the salt of DBN (1,5-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-5-alkene).The salt of DBU and DBN and the mutual solubility of all kinds of SOLVENTS are all good, compare with using the situation of existing tertiary amine or mineral-type basic catalyst, under the condition of milder, also can improve reaction yield.
Salt as DBU and DBN, can enumerate such as DBU-phenolate, DBU-octylate, DBU-oleate, DBU-tosilate, DBU-formate, DBN-phenolate, DBN-octylate, DBN-oleate, DBN-tosilate, DBN-formate methylamine etc., in addition also can enumerate, the salt etc. of amidine alkali and guanidine alkali.In addition the highly basic salt that, takes off proton-effect so long as dissolve in organic solvent also can be used.Described these temperature sensibility catalyzer can be used alone and also can two or more mixing use.Further, so long as can promote to carry out with acryl the catalyzer of addition reaction, be not limited to above-mentioned temperature sensibility catalyzer, can with performance catalyst activity method together with use.
The amount of allocating into of temperature sensibility catalyzer is with respect to the multifunctional polymerizable compound with two above acryls of 100 weight parts, preferably in the scope of 5-20 weight part.By within the scope of this, the resin combination rubber viscosity of more having difficult labour when the state of one-step solidification.
By irradiation ultraviolet radiation or electron rays isoreactivity energy-ray, resin combination of the present invention is carried out to regelate.In the situation that carrying out ultraviolet curing, can use extra-high-pressure mercury vapour lamp, high pressure mercury vapour lamp, Cooper-Hewitt lamp, carbon arc lamp, metal halide lamp etc., in the wavelength region of 100-400nm, preferred 200-400nm, irradiate and there is 50-300mJ/cm
2the ultraviolet ray of energy.In order to prevent solidifying obstacle, also can irradiate with rare gas elementes such as nitrogen.
In the situation that being cured by ultraviolet ray, the multifunctional polymerizable compound with two above acryls preferably adding with respect to 100 weight parts is the ultraviolet hardening initiator of 3-10 weight part.By making addition more than 3 weight parts, can make to be difficult for removing residual glue viscosity after thermofixation, by making addition below 10 weight parts, can suppress excessive curing reaction, thereby guarantee formability.
As ultraviolet hardening initiator, can enumerate for example 1-hydroxy-cyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, xanthone, Fluorenone, phenyl aldehyde, fluorenes, anthraquinone, triphenylamine, carbazole, 3-methyl acetophenone, 4-chlorobenzophenone, 4,4 '-dimethoxy-benzophenone, 4,4 '-diaminobenzophenone, tetramethyldiaminobenzophenone (Michler ' s ketone), bitter almond oil camphor propyl ether, ethoxybenzoin, benzil dimethyl ketal (benzyl dimethyl ketal), 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-third-1-ketone, 2-hydroxyl-1-[4-[4-(2-hydroxy-2-methyl-propionyl)-phenmethyl]-phenyl]-2-methyl-propyl-1-ketone, 2-hydroxy-2-methyl-1-phenyl third-1-ketone, thioxanthone, diethyl thioxanthone, ITX, CTX, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl-propyl-1-ketone, TMDPO, two-(2,6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxides etc., as enumerating Irgacure127 in commercial goods, 184, 369, 651, 500, 819, 907, 2959 (are above チバ ジヤパン company and manufacture, trade(brand)name) etc.These ultraviolet hardening initiators also can two or more common uses.
In addition,, in the situation that resin combination being cured by electron rays, can use known electron beam irradiation device.The irradiation dose of electron rays is preferably 10-200kGy, more preferably 30-100kGy.By using irradiation dose more than 10kGy, can guarantee that resin combination is cured, by using the irradiation dose below 200kGy, can reduce the load of electron beam irradiation device, be economical.
(2) hard-coating agent of the present invention
Hard-coating agent of the present invention be characterized as the resin combination that contains above-mentioned (1).The hard coat that uses hard-coating agent of the present invention to form is carrying out under the state after one-step solidification, is also difficult for producing the flexibility in crack while not only having moulding, is also difficult for producing tackiness.In addition, the hard coat that uses hard-coating agent of the present invention to form is carrying out under the state after regelate, and hardness and scuff resistance are all good.
Hard-coating agent of the present invention can be the resin combination itself of above-mentioned (1), also can suitably add other compositions.
(3) film of the present invention (moulding film)
Film of the present invention is characterised in that, is formed with the hard coat that the resin combination by above-mentioned (1) forms on film substrate.
Film of the present invention for example can be hard coat in having carried out the form of the state after one-step solidification.The hard coat that forms film of the present invention has the flexibility that is difficult for producing crack.Therefore, film of the present invention can not produce crack on hard coat, and may be molded to deep-draw or complicated structure that designability is good.
In addition, even if the hard coat that forms film of the present invention is also difficult for producing tackiness in not carrying out the state of regelate, the bonding in the time of therefore can preventing bonding between film and moulding between film and mold.Further, the hardness of the hard coat after regelate and scuff resistance are all good.
Film of the present invention preferably has protective layer in the layer above hard coat.Even do not there is enough hardness in having carried out the hard coat of the state after one-step solidification, by possessing protective layer, when film forming for example, be also difficult for producing scar on hard coat.Protective layer can be by for example making described solvent evaporates fall to form by dissolving or being dispersed in resin-coated in solvent after on hard coat.Thus, do not worry can as using the situation of the protective layer being formed by the film etc. of having used tackiness agent, adhesive residue is on the surface of hard coat, thus generation problem of appearance.
The resin that is used to form protective layer is such resin preferably, and described resin has the hardness of the hard coat of protecting as far as possible one-step solidification state, good with the adaptation of hard coat, and when hard coat is peeled off not at remained on surface.As such resin, can enumerate polyvinyl acetal resin such as polyvinyl alcohol (PVA), polyethylene oxide (PEO), polyvinyl alcohol modification, sodium polyacrylate etc., as the resin being dispersed in solvent, can enumerate vinyl-acetic ester emulsion, ethane-acetic acid ethyenyl ester (EVA) emulsion, ACRYLIC EMULSION, vinylformic acid styrene emulsion, vinylidene chloride emulsion, carbamate emulsion, decentralized fluoro-resin etc.Preferably polyethylene alcohol wherein.
In addition, in the resin of formation protective layer, also can add dyestuff, pigment, matting agent, antistatic agent, defoamer, flow agent, tackifier, pH adjusting agent, water-fast mixture, linking agent etc.The protective layer forming on hard coat can be removed aptly before regelate.
For film of the present invention, for example, film substrate is carried out to assisted ejection and processes (From type and process), it can become transfer film that can transfer printing hard coat.In this case, can be at the surface transfer hard coat of miscellaneous part (also can be other films).As assisted ejection, process, can enumerate such as siloxane treated etc.
Film of the present invention can be also the film of compression moulding in section bar for example.Even if form the hard coat of film of the present invention, when moulding, be also difficult for producing crack.
Film of the present invention also can be for hard coat be in having carried out the state of regelate by active energy beam.In the time of under this state, the hardness of hard coat and scuff resistance are all good.
As the film substrate in film of the present invention, can enumerate for example polyethylene terephthalate thin film, polybutylene terephthalate film, Polyethylene Naphthalate film, polyethylene film, polypropylene film, glassine paper, diacetyl cellulose film, tri acetyl cellulose film, ethanoyl cellulose butylate film, polyvinyl chloride film, poly-inclined to one side 1, 1-Ethylene Dichloride film, PVA (PVOH) FILM, vinyl-vinyl acetate copolymer film, polystyrene film, polycarbonate film, poly-methyl pentene film, polysulphone film, poly (ether ether ketone) film, polyethersulfone film, polyetherimide film, Kapton, fluorine resin film, nylon film, acrylic resin film etc.
In addition, in order to improve the adaptation of film substrate and resin combination, also can by sand-blast or solvent treatment method etc., carry out concave-convex surface processing to film substrate, or carry out the surface treatment of surface oxidation treatment such as Corona discharge Treatment, chromic acid processing, flame treating, hot blast processing, ozone-ultraviolet line radiation treatment etc.
Method for coating resin composition on film substrate is not particularly limited, and can use known method, such as photogravure cladding process, excellent painting method, scraper cladding process, rolling method, scraper plate cladding process, smooth out with the fingers Tu Fa etc.The mode that for example, thickness after the dry solidification of take is processed is 1-200 μ m is coated with, dry solidification is processed.
(4) manufacture method of formed body of the present invention
The manufacture method of formed body of the present invention is characterised in that, the film of described (3) is suppressed on section bar, and with active energy beam, made described hard coat carry out regelate after the demoulding.
According to the present invention, when moulding, hard coat is difficult for producing crack.In addition, even if be also difficult for to produce tackiness under the state of hard coat in not carrying out regelate, the bonding in the time of therefore can preventing bonding between film and moulding between film and mold.Further, the hardness of the hard coat after regelate and scuff resistance are all good.
Based on Fig. 1 (a)-(d), the specific examples of the manufacture method of the film forming body (formed body) 6 the present invention relates to is described.First, coating resin composition 1 (Fig. 1 (a)) on film substrate 9.Now, resin combination 1 is liquid.Then, by heat drying resin combination 1, make its thermofixation, form hard coat 2, thereby obtain film 5 (Fig. 1 (b)) for moulding.Now, hard coat 2 is solid, the state in one-step solidification.Then, film 5 for (not shown) extrusion molding on section bar, and after the demoulding (Fig. 1 (c)) to its irradiation ultraviolet radiation, thereby make hard coat 2 carry out regelate, obtain film forming body 6 (Fig. 1 (d)).
Accompanying drawing explanation
Fig. 1 (a)-(d) for showing the explanatory view of the manufacture method of film forming body.
Nomenclature
1... resin combination; 2... hard coat; 5... moulding film; 6... film forming body; 9... film substrate
Embodiment
Embodiments of the present invention are described.
Embodiment 1
(a) manufacture of resin combination (hard-coating agent)
Allocate table 1 into each composition shown in table 3, manufacture the resin combination of embodiment 1-1 to 1-18 and comparative example 1 to 2.In addition, table 1 to table 3 has shown the amount of allocating into converting with solids component.Resin combination is two doses of forms of A agent, B agent, manufactures respectively A agent, B agent.A agent contains the composition that table 1 is recorded to A agent one hurdle in table 3, is to take the solution that solids component that MEK (methylethylketone) is solvent is 40 % by weight.B agent contains the composition that table 1 is recorded to B agent one hurdle in table 3, is to take the solution that toluene is solvent.
While using resin combination, A agent is mixed with weight ratio with B agent at 1: 1.In addition, the solids component ratio of B agent is set as: when A agent is mixed with weight ratio with B agent at 1: 1, by solids component, convert, the allocation ratio of resin combination is that table 1 is to the allocation ratio shown in table 3.
Table 1
Table 2
Table 3
A secondary
Solidify
Rear
In addition, at table 1 to table 3, the trade(brand)name of the urethane acrylate that U-15HA Wei Xinzhong village chemical industry (strain) society manufactures.PVC one system セ Star ト 371 is the trade(brand)name of the acryl acrylate of waste river chemical industry (strain) society manufacture.ア ロ ニ Star Network ス M7300K is the trade(brand)name of the polyester acrylate of synthetic (strain) society in East Asia manufacture.
DPHA (dipentaerythritol acrylate), U-15HA, PVC one system セ Star ト 371 and ア ロ ニ Star Network ス M7300K are equivalent to have the multifunctional polymerizable compound of two above acryls separately.
In addition, irg2959 is the trade(brand)name of the UV initiator of チ バ ジ ヤ パ Application manufacture.BYK310 is the trade(brand)name of the flow agent of PVC Star Network ケ ミYi ジヤパン company manufacture.
In addition, DETA (dimethylene triamine), TETA (trimethylene tetramine) and PETA (pentamethylene hexamine) are equivalent to low molecular weight amine separately.
In addition Port リ メ Application ト NK-350 and the Port リ メ Application ト NK-380 trade(brand)name of the polyamine that (strain) Japanese catalyst society manufactures of respectively doing for oneself.
In addition, U-CAT SA 1 is the trade(brand)name of the DBU-phenolate of サ Application ア Block ロ (strain) society manufacture.U-CAT SA 102 is the trade(brand)name of the CBU-octylate of サ Application ア Block ロ (strain) society manufacture.U-CAT 1102 is the trade(brand)name of the DBN-octylate of サ Application ア Block ロ (strain) society manufacture.
U-CAT SA 1, U-CAT SA 102 and U-CAT 1102 are equivalent to temperature sensibility catalyzer separately.
(b) manufacture of film and formed body
By resin combination of manufacturing in above-mentioned (a) the PET film of thick 100 μ m (Japan (strain) society of twisting flax fibers and weaving manufactures, trade(brand)name: コ ス モ シ ヤ イ Application A4300-188) upper take solidify the mode that rear film thickness is 5 μ m and be coated with.
Then, the resin combination after coating, at 110 ℃ dry 3 minutes (one-step solidifications), is formed to the hard coat of solid, thereby obtains moulding film.Then, this moulding is suppressed on section bar to the demoulding with film.Then use ultraviolet irradiation machine, exposure intensity is 200mJ/cm
2ultraviolet ray, carry out the ultraviolet curing (regelate) of hard coat, thereby make film forming body.
(c) evaluation to resin combination and moulding use film
For resin combination and the moulding film manufactured in described (a) to (b), check its outward appearance, storage period, tackiness, formability and pencil hardness.The method of inspection and judgement criteria are as follows.
(outward appearance) is with visual observation appearance of film.The clarification of filming is evaluated as zero, and albefaction is evaluated as *.
(storage period) measures resin combination at normal temperatures until the gelation time used.
(tackiness) be coating resin composition on PET film, at 110 ℃, after dry 3 minutes, with forefinger touching resin combination, judges.Judging criterion is as follows.In addition,, only for comparative example 2, after resin combination regelate, also carry out same check.
5: completely non-glued
4: gluing hardly
3: roughly non-glued
2: slightly gluing
1: residual gluing
(formability) by film for moulding (state of hard coat in one-step solidification) in moulding with suppressing on mold, do not crack and be evaluated as zero, crack be evaluated as *.In addition,, only for comparative example 2, the moulding after regelate is also carried out to same check with film.
(pencil hardness), for film for moulding (state of hard coat in regelate), carries out pencil hardness test according to JIS K5400.Test is carried out in the situation that pencil hardness is 2H and H.In addition, in each pencil hardness, carry out 5 tests.The number of times that does not produce scar on hard coat in 5 times is documented in to above-mentioned table 1 to table 3.
Evaluation result is presented at above-mentioned table 1 to table 3.If table 1 is to as shown in table 3, the hard coat outward appearance of embodiment 1-1 to 1-18 is good, and the storage period of resin combination is long, and the hard coat under the state after one-step solidification does not produce tackiness, and moulding is also good by the formability of film.In addition, the hardness of the hard coat under the state after regelate is high.
Particularly, the embodiment 1-1 that is combined with low molecular weight amine and polyamine compares with the embodiment 1-8 to 1-9 that only allocates low molecular weight amine and one of polyamine into, more difficult generation tackiness.In addition, the embodiment 1-1 that has allocated temperature sensibility catalyzer into compares with the embodiment 1-10 that does not allocate temperature sensibility catalyzer into, more difficult generation tackiness.
Embodiment 2
Substantially similarly manufacture moulding film with (a) to (b) of above-described embodiment 1.But in the present embodiment 2, forming hard coat and making it carry out, after one-step solidification, on hard coat, being coated with PVA, forming protective layer.Then, similarly obtain film forming body with above-described embodiment 1.Finally, peel off protective layer.In the present embodiment 2, because be has formed under the state of protective layer to carry out moulding on hard coat, be therefore difficult for producing scar on hard coat.In addition, peel off after protective layer, on the surface of hard coat, there is no remaining trace completely.
Embodiment 3
Substantially similarly manufacture moulding film with (a) to (b) of above-described embodiment 1.But in the present embodiment 3, forming hard coat and it has been carried out after one-step solidification, on hard coat, adhering to the film of having used tackiness agent, forming protective layer.Then, similarly obtain film forming body with above-described embodiment 1.Finally, peel off protective layer.In the present embodiment 3, because be has formed under the state of protective layer to carry out moulding on hard coat, be therefore difficult for producing scar on hard coat.But, peel off after protective layer slightly residual tackiness agent on the surface of hard coat.
Embodiment 4
Substantially similarly manufacture moulding film with (a) to (b) of above-described embodiment 1.But in the present embodiment, as the film substrate of coating resin composition, use assisted ejection (From type) PET film (Japan twist flax fibers and weave (strain) manufacture, trade(brand)name: TN110).This assisted ejection PET film has been carried out to assisted ejection processing, then, can make layer (hard coat) the easily demoulding being formed by resin combination.
The moulding of the present embodiment can be used as transfer film with film.Transfer film for example can as described belowly be used.First, make the side and the formed material side butt that have formed hard coat in film for moulding, carry out moulding.Now, the state of hard coat after one-step solidification.Then, take off assisted ejection PET film.Now, in the surface adhesion of formed material, hard coat.Then irradiation ultraviolet radiation, makes hard coat carry out regelate.In addition, the moulding of the present embodiment also can be used for (in mold) injection moulding in mould with film.
In addition, the invention is not restricted to above-described embodiment, within not departing from scope of the present invention, certainly can implement in every way the present invention.
Claims (9)
1. the manufacture method of formed body, has following steps:
(i) by comprising the resin combination that there is the multifunctional polymerizable compound of two above acryls and can carry out the compound of addition reaction with acryl, be coated on the step on film substrate;
(ii) thus will carry out through coated thin film heating the step of one-step solidification;
(iii) by suppressing on section bar through the described film of one-step solidification, thereby and this section bar demoulding is carried out to the step of forming process to described film;
(iv), to the described film irradiation ultraviolet radiation through forming process, described film is carried out to the step of regelate.
2. the manufacture method of the formed body of claim 1, is characterized in that having protective layer in the layer above hard coat.
3. the film using in the manufacture method of the formed body in claim 1.
4. film claimed in claim 3, is characterized in that, in the layer above described hard coat, has protective layer.
5. film claimed in claim 4, is characterized in that, described protective layer is by making described solvent evaporates fall to form by dissolving or being dispersed in resin-coated in solvent after on described hard coat.
6. film claimed in claim 5; it is characterized in that; the resin that forms described protective layer is selected from the polyvinyl acetal resin of polyvinyl alcohol, polyethylene oxide, polyvinyl alcohol modification, sodium polyacrylate, vinyl-acetic ester emulsion, ethylene-vinyl acetate emulsion, ACRYLIC EMULSION, vinylformic acid styrene emulsion, vinylidene chloride emulsion, carbamate emulsion, decentralized fluoro-resin.
7. film claimed in claim 3, is characterized in that, described film substrate is carried out to assisted ejection processing, can transfer printing described in hard coat.
8. film claimed in claim 4, is characterized in that, described film substrate is carried out to assisted ejection processing, can transfer printing described in hard coat.
9. the film described in claim 5 or 6, is characterized in that, described film substrate is carried out to assisted ejection processing, can transfer printing described in hard coat.
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008075177 | 2008-03-24 | ||
| JP2008-075177 | 2008-03-24 | ||
| JP2008-075174 | 2008-03-24 | ||
| JP2008075174 | 2008-03-24 | ||
| JP2008-079668 | 2008-03-26 | ||
| JP2008079668 | 2008-03-26 | ||
| JP2008224189 | 2008-09-02 | ||
| JP2008-224208 | 2008-09-02 | ||
| JP2008-224189 | 2008-09-02 | ||
| JP2008224208 | 2008-09-02 | ||
| PCT/JP2009/055833 WO2009119588A1 (en) | 2008-03-24 | 2009-03-24 | Resin composition, hard-coating agent, film, and method for production of molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101981068A CN101981068A (en) | 2011-02-23 |
| CN101981068B true CN101981068B (en) | 2014-10-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200980110485.7A Expired - Fee Related CN101981068B (en) | 2008-03-24 | 2009-03-24 | Resin composition, hard-coating agent, film, and method for production of molded article |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5654207B2 (en) |
| KR (1) | KR101579276B1 (en) |
| CN (1) | CN101981068B (en) |
| TW (1) | TWI449713B (en) |
| WO (1) | WO2009119588A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5422787B2 (en) * | 2009-11-13 | 2014-02-19 | 名阪真空工業株式会社 | LAMINATED FILM AND METHOD FOR PRODUCING MOLDED BODY |
| KR101291937B1 (en) * | 2011-04-15 | 2013-07-31 | (주)엘지하우시스 | Hard-coating composition and sheet for forming hard-coating with excellent low temperature formability and slip property |
| CN103631459B (en) * | 2012-08-26 | 2016-12-21 | 宝宸（厦门）光学科技有限公司 | Touch-control sensing layer and manufacture method thereof |
| JPWO2014175312A1 (en) * | 2013-04-26 | 2017-02-23 | 富士フイルム株式会社 | TRANSFER MATERIAL, SUBSTRATE WITH TRANSFER LAYER AND TOUCH PANEL, METHOD FOR PRODUCING THEM, AND INFORMATION DISPLAY DEVICE |
| US10292309B2 (en) * | 2013-11-12 | 2019-05-14 | Jnc Corporation | Heat sink |
| FR3022544B1 (en) * | 2014-06-23 | 2018-01-05 | Arkema France | MULTIFUNCTIONAL ACRYLIC OLIGOMERS OF BRANCHED STRUCTURE, BY POLYADDITION BETWEEN AMINES AND MULTIFUNCTIONAL ACRYLATES. |
| JPWO2021140875A1 (en) * | 2020-01-08 | 2021-07-15 | ||
| WO2024080249A1 (en) * | 2022-10-11 | 2024-04-18 | 株式会社レゾナック | Resin film-forming material and resin film |
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| CN1427033A (en) * | 2001-12-21 | 2003-07-02 | 大日本油墨化学工业株式会社 | Curable resin composition and process for preparing low-polymer containing acrylyl and substituted methacrylic acid radical |
| CN1568341A (en) * | 2001-10-12 | 2005-01-19 | 阿什兰公司 | Self-photoinitiating multifunctional acrylates |
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| EP0160824B2 (en) * | 1984-04-04 | 1994-08-03 | Hoechst Aktiengesellschaft | Reaction product of olefinically unsaturated compounds with active hydrogen compounds, process for their preparation and 2-component coating systems based thereon |
| JPH0339366A (en) * | 1989-07-06 | 1991-02-20 | Mitsubishi Petrochem Co Ltd | Covering material composition for hand coat |
| DE4212485A1 (en) * | 1992-04-14 | 1993-10-21 | Basf Lacke & Farben | Addition products, radiation-curable coating compositions based on the addition products and their use for wood coating and paper coating |
| JPH0892369A (en) * | 1994-07-29 | 1996-04-09 | Toyo Ink Mfg Co Ltd | Curable liquid resin composition and production of cured product therefrom |
| DE19627826A1 (en) * | 1996-07-10 | 1998-01-15 | Bayer Ag | New polyamines and their use in aqueous paints and coatings |
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- 2009-03-24 CN CN200980110485.7A patent/CN101981068B/en not_active Expired - Fee Related
- 2009-03-24 JP JP2009072151A patent/JP5654207B2/en not_active Expired - Fee Related
- 2009-03-24 WO PCT/JP2009/055833 patent/WO2009119588A1/en active Application Filing
- 2009-03-24 KR KR1020107023668A patent/KR101579276B1/en not_active IP Right Cessation
- 2009-03-24 TW TW098109467A patent/TWI449713B/en not_active IP Right Cessation
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| CN1568341A (en) * | 2001-10-12 | 2005-01-19 | 阿什兰公司 | Self-photoinitiating multifunctional acrylates |
| CN1427033A (en) * | 2001-12-21 | 2003-07-02 | 大日本油墨化学工业株式会社 | Curable resin composition and process for preparing low-polymer containing acrylyl and substituted methacrylic acid radical |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010084120A (en) | 2010-04-15 |
| CN101981068A (en) | 2011-02-23 |
| TW201000499A (en) | 2010-01-01 |
| KR101579276B1 (en) | 2015-12-21 |
| KR20100139060A (en) | 2010-12-31 |
| JP5654207B2 (en) | 2015-01-14 |
| TWI449713B (en) | 2014-08-21 |
| WO2009119588A1 (en) | 2009-10-01 |
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