WO2009119588A1 - 樹脂組成物、ハードコート剤、フィルム、及び成型体の製造方法 - Google Patents

樹脂組成物、ハードコート剤、フィルム、及び成型体の製造方法 Download PDF

Info

Publication number
WO2009119588A1
WO2009119588A1 PCT/JP2009/055833 JP2009055833W WO2009119588A1 WO 2009119588 A1 WO2009119588 A1 WO 2009119588A1 JP 2009055833 W JP2009055833 W JP 2009055833W WO 2009119588 A1 WO2009119588 A1 WO 2009119588A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
hard coat
resin composition
coat layer
film according
Prior art date
Application number
PCT/JP2009/055833
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
晴彦 間瀬
剛 西野
Original Assignee
アイカ工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by アイカ工業株式会社 filed Critical アイカ工業株式会社
Priority to CN200980110485.7A priority Critical patent/CN101981068B/zh
Publication of WO2009119588A1 publication Critical patent/WO2009119588A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a resin composition, a hard coat agent, a film, and a method for producing a molded body.
  • thermosetting resin has been used in a membrane switch of home appliances and a dummy can of a vending machine.
  • a molding film in which an ultraviolet curable resin that is superior in scratch resistance as compared with a thermosetting resin is coated and cured has become widespread.
  • electronic equipment casings and automobile interior materials such as mobile phones, portable music players, and touch panels are required to have hardness, scratch resistance, contamination resistance, glossiness, etc. Films for coating and curing are being applied (see Patent Documents 1 to 3).
  • thermosetting resin has low hardness and scratch resistance, is easily scratched, and the appearance is remarkably deteriorated.
  • a molding film coated and cured with an ultraviolet curable resin is rigid and easily cracked. Therefore, it has poor moldability and can only be used for molding a relatively flat structure.
  • the present invention has been made in view of the above points, and an object thereof is to provide a resin composition, a hard coat agent, a film, and a method for producing a molded body having high hardness and scratch resistance and good moldability.
  • the resin composition of the present invention is characterized by containing a polyfunctional polymerizable compound having two or more acryloyl groups and a compound capable of undergoing an addition reaction to an acryloyl group.
  • the resin composition of the present invention in a primary cured state, has flexibility that is difficult to crack even when molded, and is less susceptible to tack.
  • the resin composition of the present invention is excellent in hardness and scratch resistance in a secondarily cured state.
  • the primary curing means an addition reaction to an acryloyl group. Secondary curing is radical polymerization by irradiating active energy rays such as ultraviolet rays and electron beams.
  • the polyfunctional polymerizable compound having two or more acryloyl groups according to the present invention has very high radical reactivity, and is superior in terms of fast curing and high hardness.
  • Examples of the polyfunctional polymerizable compound having two or more acryloyl groups include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, and hydroxypivalate neodymium.
  • the polyfunctional polymerizable compound having two or more acryloyl groups may be a monomer or a prepolymer, and may be urethane acrylate, epoxy acrylate, polyester acrylate, or the like.
  • the compound capable of addition reaction to the acryloyl group used in the present invention is a compound capable of addition reaction with a polyfunctional polymerizable compound having two or more acryloyl groups. Since the resin composition is primarily cured (B-stage) by this addition reaction, the tack of the resin composition disappears or decreases. Utilizing this, the application of the resin composition to the film and the provision of conditions that promote the addition reaction can prevent blocking between films and blocking between the film and the mold during molding.
  • the compound capable of undergoing addition reaction to the acryloyl group may be any compound having nucleophilicity, but specifically, an amine compound is preferable.
  • amine compound those having a primary or secondary amine, for example, methylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, aniline, phenethylamine, amantadine, piperazine
  • low molecular weight amines such as amino group-containing silane coupling agents.
  • the low molecular weight amine in the present invention means ethylenediamine derivatives such as DETA (diethylenetriamine), TETA (triethylenetetramine), PEHA (pentaethylenehexamine), and the molecular weight is preferably in the range of 50 to 400, for example. It is.
  • a polyamine having an amine as a repeating structure can also be used.
  • a low molecular weight amine and a polyamine in combination, the curability of the resin composition can be easily adjusted.
  • tack is less likely to occur when the resin composition is in a primary curing state.
  • the molecular weight of the polyamine is preferably in the range of 10,000 to 200,000, for example.
  • the amount of the amine compound used depends on the amine value of the amine compound used, but is preferably in the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the polyfunctional polymerizable compound having two or more acryloyl groups.
  • the range of 0.5 to 30 parts by weight is more preferable, and the range of 5 to 25 parts by weight is particularly preferable.
  • the curability can be improved by increasing the compounding amount of the amine compound or increasing the proportion of the polyamine in the amine compound.
  • the pot life of the resin composition is short, the pot life can be extended by reducing the compounding amount of the amine compound or reducing the proportion of polyamine in the amine compound.
  • the higher the amine value the higher the reactivity of the amine compound, the smaller the amount of amine compound added, and the better the surface properties.
  • a temperature-sensitive catalyst By blending a temperature-sensitive catalyst with a compound capable of undergoing addition reaction to the acryloyl group, it is easy to achieve both primary curability and pot life of the resin composition. That is, since the temperature-sensitive catalyst has no (or low) catalytic activity at room temperature, the pot life of the resin composition can be lengthened, and the primary curability can be improved because it exhibits its activity rapidly at high temperatures. . Moreover, when a temperature sensitive catalyst is mix
  • thermosensitive catalyst salts of DBU (diazabicycloundecene) or DBN (diazabicyclononene) which are strong bases are particularly preferable.
  • DBU and DBN salts are excellent in compatibility with various solvents, and can improve the reaction yield under milder conditions than using conventional tertiary amines and inorganic basic catalysts.
  • salts of DBU and DBN include, for example, DBU-phenol salt, DBU-octylate, DBU-oleate, DBU-p-toluenesulfonate, DBU-formate, DBN-phenol salt, DBN-octylic acid Salts, DBN-oleate, DBN-p-toluenesulfonate, DBN-formate methylamine, and the like, and salts of amidine base and guanidine base.
  • any strong base salt that is soluble in an organic solvent and deprotonates can be used.
  • These temperature-sensitive catalysts may be used alone or in admixture of two or more.
  • the catalyst is not limited to the temperature-sensitive catalyst as long as it can promote the addition reaction to the acryloyl group, and can be used together with a means capable of exhibiting catalytic activity.
  • the amount of the temperature-sensitive catalyst is preferably in the range of 5 to 20 parts by weight with respect to 100 parts by weight of the polyfunctional polymerizable compound having two or more acryloyl groups. By being in this range, when the resin composition is in a primary curing state, tack is less likely to occur.
  • the resin composition of the present invention is secondarily cured by irradiating active energy rays such as ultraviolet rays and electron beams.
  • an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp or the like is used, and an ultraviolet ray having an energy of 50 to 300 mJ / cm 2 in a wavelength region of 100 to 400 nm, preferably 200 to 400 nm.
  • an ultraviolet ray having an energy of 50 to 300 mJ / cm 2 in a wavelength region of 100 to 400 nm, preferably 200 to 400 nm.
  • irradiation may be performed under an inert gas such as nitrogen gas.
  • Examples of the ultraviolet curable initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4 -Chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl Propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- [4- ( 2-hi Droxy-2-methyl-propionyl) -benzyl]
  • the hard coat agent of the present invention is characterized by including the resin composition of (1).
  • the hard coat layer formed using the hard coat agent of the present invention in a primary cured state, has flexibility that is difficult to crack even if molded, and is less likely to cause tack.
  • the hard coat layer formed using the hard coat agent of the present invention is excellent in hardness and scratch resistance in a secondary cured state.
  • the hard coating agent of the present invention may be the resin composition (1) as it is, or may be appropriately added with other components.
  • Film of the present invention film for molding
  • the film of the present invention is characterized in that a hard coat layer comprising the resin composition (1) is formed on a film substrate.
  • the film of the present invention can be, for example, in a state where the hard coat layer is primarily cured.
  • the hard coat layer constituting the film of the present invention has a flexibility that is difficult to crack. Therefore, the film of the present invention can be molded into a deep drawing or a complicated structure having excellent design properties without causing cracks in the hard coat layer. Further, the hard coat layer constituting the film of the present invention is less likely to cause tackiness even in a state where it is not secondarily cured, so that blocking between films and blocking between the film and the mold during molding can be prevented. Furthermore, the hard coat layer after secondary curing is excellent in hardness and scratch resistance.
  • the film of the present invention preferably includes a protective layer in an upper layer than the hard coat layer.
  • the hard coat layer in the primary cured state does not have sufficient hardness, the hard coat layer is hardly damaged when the film is formed, for example, by providing the protective layer.
  • the protective layer can be formed, for example, by applying a resin dissolved or dispersed in a solvent to the hard coat layer and then volatilizing the solvent. By doing so, the pressure-sensitive adhesive remains on the surface of the hard coat layer as in the case of using a protective layer made of a film with a pressure-sensitive adhesive or the like, and there is no possibility of causing a problem in appearance.
  • the resin used to form the protective layer has a hardness sufficient to protect the hard-cured layer in the first-cured state, has good adhesion to the hard-coat layer, and further on the surface when peeling from the hard-coat layer. Resins that do not remain are preferred. Examples of such resins include polyvinyl alcohol (PVA), polyethylene oxide (PEO), polyvinyl alcohol-modified polyvinyl acetal resin, sodium polyacrylate, and the like.
  • PVA polyvinyl alcohol
  • PEO polyethylene oxide
  • polyvinyl alcohol-modified polyvinyl acetal resin sodium polyacrylate, and the like.
  • Resins dispersed in a solvent include vinyl acetate emulsion, ethylene acetate Examples include vinyl (EVA) emulsion, acrylic emulsion, acrylic styrene emulsion, vinylidene chloride emulsion, urethane emulsion, and dispersion type fluororesin. Of these, polyvinyl alcohol is preferred.
  • dyes, pigments, matting agents, antistatic agents, antifoaming agents, leveling agents, thickeners, pH adjusters, water resistance agents, crosslinking agents, etc. may be added to the resin forming the protective layer.
  • the protective layer formed on the hard coat layer can be appropriately removed before the secondary curing.
  • the film of the present invention can be formed into a transfer film capable of transferring a hard coat layer by, for example, subjecting a film substrate to a release treatment.
  • the hard coat layer can be transferred to the surface of another member (which may be another film).
  • a mold release process a silicone process etc. are mentioned, for example.
  • the film of the present invention may be, for example, pressed and molded by a mold material. Even if the hard coat layer constituting the film of the present invention is molded, it is difficult to crack.
  • the film of the present invention may be, for example, in a state where the hard coat layer is secondarily cured by active energy rays. In this state, the hard coat layer is excellent in hardness and scratch resistance.
  • polyethylene terephthalate film for example, polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, Polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, polyether sulfone film, polyether Imide film, polyimide film, fluorine resin fill , Nylon film, acrylic resin film or the like.
  • the surface of the film substrate is roughened by sandblasting or solvent treatment, or corona discharge treatment, chromic acid treatment, flame treatment.
  • Surface treatment such as surface oxidation treatment such as hot air treatment or ozone / ultraviolet irradiation treatment may be performed.
  • the method for producing the molded product of the present invention is to press the film of (3) against a mold material, and after demolding, secondarily cure the hard coat layer with active energy rays. It is characterized by that. According to the present invention, it is difficult for the hard coat layer to break during molding.
  • the hard coat layer is not easily tacky even in a state where it is not secondarily cured, it is possible to prevent blocking between films and blocking between a film and a mold during molding. Furthermore, the hard coat layer after secondary curing is excellent in hardness and scratch resistance.
  • FIGS. 1 A specific example of a method for producing a film molded body (molded body) 6 according to the present invention will be described with reference to FIGS.
  • the resin composition 1 is apply
  • the resin composition 1 is thermally cured by heating and drying to form a hard coat layer 2 to obtain a molding film 5 (FIG. 1B).
  • the hard coat layer 2 is solid and is in a state of primary curing.
  • the molding film 5 is pressed against a mold material (not shown), and after demolding (FIG. 1 (c)), the hard coat layer 2 is secondarily cured by irradiating with ultraviolet rays to obtain a film molding 6. (FIG. 1 (d)).
  • the components shown in Tables 1 to 3 were blended to produce the resin compositions of Examples 1-1 to 1-18 and Comparative Examples 1-2.
  • Tables 1 to 3 show blending amounts in terms of solid content.
  • the resin composition is a two-agent type of agent A and agent B, and agent A and agent B were produced, respectively.
  • Agent A is a solution having a solid content of 40% by weight containing the components described in the column of Agent A in Tables 1 to 3 and using MEK (methyl ethyl ketone) as a solvent.
  • Agent B is a solution containing the components described in the column of Agent B in Tables 1 to 3 and using toluene as a solvent.
  • the agent A and the agent B are mixed at a weight ratio of 1: 1.
  • the solid content ratio of the B agent is such that when the A agent and the B agent are mixed at a weight ratio of 1: 1, the compounding ratio of the resin composition is as shown in Tables 1 to 3 in terms of solid content. It is set to be.
  • U-15HA is a trade name of urethane acrylate manufactured by Shin-Nakamura Chemical Co., Ltd.
  • the beam set 371 is a trade name of acrylic acrylate manufactured by Arakawa Chemical Industries, Ltd.
  • Aronix M7300K is a trade name of polyester acrylate manufactured by Toa Gosei Co., Ltd.
  • DPHA dipentaerythritol hexaacrylate
  • U-15HA beam set 371, and Aronix M7300K each correspond to a polyfunctional polymerizable compound having two or more acryloyl groups.
  • irg2959 is a trade name of a UV initiator manufactured by Ciba Japan.
  • BYK310 is a trade name of a leveling agent manufactured by Big Chemie Japan Co., Ltd.
  • DETA diethylenetriamine
  • TETA triethylenetetramine
  • PETA penentaethylenehexamine
  • Poliment NK-350 and Poliment NK-380 are trade names of polyamines manufactured by Nippon Shokubai Co., Ltd.
  • U-CAT SA 1 is a trade name of DBU-phenol salt manufactured by San Avro Corporation.
  • U-CAT SA 102 is a trade name of CBU-octylate manufactured by San Avro Corporation.
  • U-CAT 1102 is a trade name of DBN-octylate manufactured by San Avro Corporation.
  • U-CAT SA 1, U-CAT SA 102, and U-CAT 1102 each correspond to a temperature sensitive catalyst.
  • Example 1-1 in which a low molecular weight amine and a polyamine were used in combination, tack was less likely to occur than in Examples 1-8 to 1-9 in which only one of a low molecular weight amine and a polyamine was blended. Further, in Example 1-1 in which the temperature-sensitive catalyst was blended, tack was less likely to occur than in Example 1-10 in which the temperature-sensitive catalyst was not blended.
  • Example 2 a film for molding was produced in the same manner as in Examples 1 (a) to (b). However, in Example 2, a hard coat layer was formed and subjected to primary curing, and then PVA was applied to the hard coat layer to form a protective layer. Thereafter, a film molded body was obtained in the same manner as in Example 1. Finally, the protective layer was peeled off. In Example 2, since the molding was performed with the protective layer formed on the hard coat layer, the hard coat layer was hardly damaged. Further, after removing the protective layer, no trace remained on the surface of the hard coat layer.
  • Example 3 a film for molding was produced in the same manner as in Examples 1 (a) to (b). However, in Example 3, after forming a hard coat layer and primarily curing it, a film with an adhesive was stuck on the hard coat layer to form a protective layer. Thereafter, a film molded body was obtained in the same manner as in Example 1. Finally, the protective layer was peeled off. In Example 3, since the molding was performed in a state where the protective layer was formed on the hard coat layer, the hard coat layer was hardly damaged. However, after the protective layer was peeled off, a little pressure-sensitive adhesive remained on the surface of the hard coat layer.
  • a film for molding was produced in the same manner as in Examples 1 (a) to (b).
  • a release PET film manufactured by Toyobo Co., Ltd., trade name: TN110
  • This release PET film has been subjected to a release treatment, and a layer (hard coat layer) made of the resin composition can be easily released later.
  • the molding film of this example can be used as a transfer film.
  • the transfer film can be used as follows, for example. First, in the molding film, the side on which the hard coat layer is formed is brought into contact with the molding material side to perform molding. At this time, the hard coat layer is in a primary cured state.
  • the release PET film is removed.
  • a hard coat layer is stuck on the surface of the molding material.
  • the hard coat layer is secondarily cured by irradiating with ultraviolet rays.
  • the molding film of this example can also be used for in-mold injection molding.
  • this invention is not limited to the said Example at all, and it cannot be overemphasized that it can implement with a various aspect in the range which does not deviate from this invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
PCT/JP2009/055833 2008-03-24 2009-03-24 樹脂組成物、ハードコート剤、フィルム、及び成型体の製造方法 WO2009119588A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200980110485.7A CN101981068B (zh) 2008-03-24 2009-03-24 树脂组合物、硬质涂覆剂、薄膜和成型体的制造方法

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
JP2008075177 2008-03-24
JP2008-075174 2008-03-24
JP2008075174 2008-03-24
JP2008-075177 2008-03-24
JP2008079668 2008-03-26
JP2008-079668 2008-03-26
JP2008-224189 2008-09-02
JP2008224189 2008-09-02
JP2008224208 2008-09-02
JP2008-224208 2008-09-02

Publications (1)

Publication Number Publication Date
WO2009119588A1 true WO2009119588A1 (ja) 2009-10-01

Family

ID=41113780

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/055833 WO2009119588A1 (ja) 2008-03-24 2009-03-24 樹脂組成物、ハードコート剤、フィルム、及び成型体の製造方法

Country Status (5)

Country Link
JP (1) JP5654207B2 (zh)
KR (1) KR101579276B1 (zh)
CN (1) CN101981068B (zh)
TW (1) TWI449713B (zh)
WO (1) WO2009119588A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011104804A (ja) * 2009-11-13 2011-06-02 Meihan Shinku Kogyo Kk 積層フィルム及び成形体の製造方法
CN103347969A (zh) * 2011-04-15 2013-10-09 乐金华奥斯有限公司 硬涂层组合物，及具有较好低温成形性和滑动性的用于形成硬涂层的片
WO2021140875A1 (ja) * 2020-01-08 2021-07-15 リケンテクノス株式会社 Ｂステージ塗膜形成用塗料、ｂステージ塗膜、及びｂステージ塗膜の製造方法
WO2024080249A1 (ja) * 2022-10-11 2024-04-18 株式会社レゾナック 樹脂膜形成材料及び樹脂膜

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103631459B (zh) * 2012-08-26 2016-12-21 宝宸（厦门）光学科技有限公司 触控感应层及其制造方法
CN105142925A (zh) * 2013-04-26 2015-12-09 富士胶片株式会社 转印材料、带有转印层的基材及触摸屏、它们的制造方法、及信息显示装置
KR20160085253A (ko) * 2013-11-12 2016-07-15 제이엔씨 주식회사 히트 싱크
FR3022544B1 (fr) * 2014-06-23 2018-01-05 Arkema France Oligomeres acryles multifonctionnels de structure ramifiee, par polyaddition entre amines et acrylates multifonctionnels.

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4994736A (zh) * 1972-09-18 1974-09-09
JPS60124673A (ja) * 1983-12-12 1985-07-03 Hitachi Chem Co Ltd 放射線硬化型感圧性接着剤組成物
JPS60226525A (ja) * 1984-04-04 1985-11-11 ヘキスト・アクチエンゲゼルシヤフト 二成分系塗料
JPH0892369A (ja) * 1994-07-29 1996-04-09 Toyo Ink Mfg Co Ltd 硬化性液状樹脂組成物およびその硬化物の製造方法
JPH08504218A (ja) * 1992-04-14 1996-05-07 ビーエーエスエフ ラッケ ウント ファルベン アクチェンゲゼルシャフト 付加生成物、この付加生成物をベースとする放射線硬化性被覆組成物、並びに木材被覆及び紙被覆のためのその使用
JPH1081746A (ja) * 1996-07-10 1998-03-31 Bayer Ag 新規なポリアミンおよび水性被覆組成物におけるその使用
JPH1192546A (ja) * 1997-09-22 1999-04-06 Toyo Ink Mfg Co Ltd 硬化性樹脂組成物
JP2000017030A (ja) * 1998-07-02 2000-01-18 Dainippon Ink & Chem Inc 活性エネルギー線硬化型水性樹脂組成物
JP2002356655A (ja) * 2001-03-27 2002-12-13 Nippon Paint Co Ltd 硬化性塗料組成物および塗膜形成方法
JP2003212975A (ja) * 2001-12-21 2003-07-30 Dainippon Ink & Chem Inc 硬化性組成物。
JP2003212926A (ja) * 2001-12-21 2003-07-30 Dainippon Ink & Chem Inc 硬化性樹脂組成物
JP2005505653A (ja) * 2001-10-12 2005-02-24 アシュランド インコーポレイテッド 自己光開始多官能アクリレート
JP2005320539A (ja) * 2004-05-03 2005-11-17 Rohm & Haas Co マイケル付加組成物
JP2007009202A (ja) * 2005-06-24 2007-01-18 Rohm & Haas Co マイケル付加反応を促進するための方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1262003A (en) * 1984-03-26 1989-09-26 Gus Nichols Solventless polymeric compositions
JPH0339366A (ja) * 1989-07-06 1991-02-20 Mitsubishi Petrochem Co Ltd ハードコート用被覆材組成物
JP4403351B2 (ja) 2000-11-29 2010-01-27 ソニー株式会社 光透過層形成用シート部材および光学記録媒体の製造方法
JP5186768B2 (ja) * 2006-06-16 2013-04-24 東洋インキＳｃホールディングス株式会社 帯電防止用硬化性組成物、硬化膜及び積層体

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4994736A (zh) * 1972-09-18 1974-09-09
JPS60124673A (ja) * 1983-12-12 1985-07-03 Hitachi Chem Co Ltd 放射線硬化型感圧性接着剤組成物
JPS60226525A (ja) * 1984-04-04 1985-11-11 ヘキスト・アクチエンゲゼルシヤフト 二成分系塗料
JPH08504218A (ja) * 1992-04-14 1996-05-07 ビーエーエスエフ ラッケ ウント ファルベン アクチェンゲゼルシャフト 付加生成物、この付加生成物をベースとする放射線硬化性被覆組成物、並びに木材被覆及び紙被覆のためのその使用
JPH0892369A (ja) * 1994-07-29 1996-04-09 Toyo Ink Mfg Co Ltd 硬化性液状樹脂組成物およびその硬化物の製造方法
JPH1081746A (ja) * 1996-07-10 1998-03-31 Bayer Ag 新規なポリアミンおよび水性被覆組成物におけるその使用
JPH1192546A (ja) * 1997-09-22 1999-04-06 Toyo Ink Mfg Co Ltd 硬化性樹脂組成物
JP2000017030A (ja) * 1998-07-02 2000-01-18 Dainippon Ink & Chem Inc 活性エネルギー線硬化型水性樹脂組成物
JP2002356655A (ja) * 2001-03-27 2002-12-13 Nippon Paint Co Ltd 硬化性塗料組成物および塗膜形成方法
JP2005505653A (ja) * 2001-10-12 2005-02-24 アシュランド インコーポレイテッド 自己光開始多官能アクリレート
JP2003212975A (ja) * 2001-12-21 2003-07-30 Dainippon Ink & Chem Inc 硬化性組成物。
JP2003212926A (ja) * 2001-12-21 2003-07-30 Dainippon Ink & Chem Inc 硬化性樹脂組成物
JP2005320539A (ja) * 2004-05-03 2005-11-17 Rohm & Haas Co マイケル付加組成物
JP2007009202A (ja) * 2005-06-24 2007-01-18 Rohm & Haas Co マイケル付加反応を促進するための方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011104804A (ja) * 2009-11-13 2011-06-02 Meihan Shinku Kogyo Kk 積層フィルム及び成形体の製造方法
CN103347969A (zh) * 2011-04-15 2013-10-09 乐金华奥斯有限公司 硬涂层组合物，及具有较好低温成形性和滑动性的用于形成硬涂层的片
WO2021140875A1 (ja) * 2020-01-08 2021-07-15 リケンテクノス株式会社 Ｂステージ塗膜形成用塗料、ｂステージ塗膜、及びｂステージ塗膜の製造方法
WO2024080249A1 (ja) * 2022-10-11 2024-04-18 株式会社レゾナック 樹脂膜形成材料及び樹脂膜

Also Published As

Publication number Publication date
CN101981068A (zh) 2011-02-23
KR20100139060A (ko) 2010-12-31
KR101579276B1 (ko) 2015-12-21
CN101981068B (zh) 2014-10-29
JP5654207B2 (ja) 2015-01-14
TWI449713B (zh) 2014-08-21
JP2010084120A (ja) 2010-04-15
TW201000499A (en) 2010-01-01

Similar Documents

Publication Publication Date Title
WO2009119588A1 (ja) 樹脂組成物、ハードコート剤、フィルム、及び成型体の製造方法
WO2009122786A1 (ja) ハードコートフィルム及び樹脂成型品
TWI363766B (en) Radiation-curable resin composition for film protective layer and, molding using the same
JP4956167B2 (ja) 塗膜形成用転写シート及びそれを用いた被覆塗膜の形成方法
JP2013060598A (ja) Ｕｖ硬化性ハイソリッド塗料組成物
JP2012210755A (ja) 成型用積層ハードコートフィルム及びその製造方法、並びに樹脂成型品の製造方法
JP2011126921A (ja) ハードコート剤組成物、ハードコートフィルム及び成形品
TW200936726A (en) Resin composition and film using it, and process for manufacturing film
KR101984338B1 (ko) 하드 코팅 조성물
KR101252326B1 (ko) 하드코팅액 조성물 및 하드 코팅 필름
JP2011011122A (ja) ハードコート積層体の製造方法
JP2009062423A (ja) 活性エネルギー線硬化型ハードコート樹脂組成物及びハードコートフィルム
JP4778249B2 (ja) 紫外線硬化型皮革調塗料組成物およびその塗料組成物により仕上げられた物品
JP6874787B2 (ja) 活性エネルギー線硬化型樹脂組成物、硬化物及び積層体
JP2011074351A (ja) 樹脂組成物および成型物
JP2011161692A (ja) 加飾成形品の製造方法
KR20100026012A (ko) 하드코팅액 조성물 및 하드 코팅 필름
JP2012210756A (ja) 成型用積層ハードコートフィルム及びその製造方法、並びに樹脂成型品の製造方法
KR101967486B1 (ko) 긴 측쇄 알킬기를 가지는 이타콘산 에스테르를 포함하는 이형필름용 수지 조성물
JP2006063163A (ja) 活性エネルギー線硬化性樹脂、活性エネルギー線硬化性樹脂組成物、コーティング剤及びプラスチック成形物
JP5990351B1 (ja) 硬化収縮チヂミ模様形成用紫外線硬化型樹脂組成物、印刷インキ、印刷物、成形品、印刷物の製造方法、及び硬化収縮チヂミ模様の形成方法
JP2009062401A (ja) 紫外線硬化型ハードコート樹脂組成物および成型用フィルム並びに成型体の製造方法
WO2021039808A1 (ja) 加飾フィルム及び加飾成型品
JP7382250B2 (ja) ポリウレアポリウレア化合物とこれを含む組成物ならびにポリウレア硬化物、およびポリウレア硬化物を含む成形フィルムならびに成形品
JP2011084687A (ja) 硬化性樹脂組成物、フィルムおよび成型方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980110485.7

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09726132

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20107023668

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 09726132

Country of ref document: EP

Kind code of ref document: A1